ASPECTS OF SAF SMELTING OF FERROCHROME

P.C. Hayes

PYROSEARCH, Pyrometallurgy Research Centre, University of Queensland, Brisbane, Queensland Q4072, Australia.
E-mail: P.Hayes@minmet.uq.edu.au

ABSTRACT

This paper provides a review of the chemical reactions occurring in the submerged arc processing of
chromite ores. The excavations of industrial furnaces have shown that the charge, as it descends through the
furnace, passes through a number of distinct reaction zones. Each zone is characterised by differing process
conditions and reaction products. The phase equilibria, reaction steps and mechanisms occurring as the
charge progresses through the furnace are examined, and the potential influences of these factors on the
process outcomes are discussed.

1. INTRODUCTION

This review of mechanisms and kinetics of chromite reduction presented is focused on providing insight into
the reactions occurring during ferrochrome smelting by submerged arc furnace technologies. The approach
taken in the review is to specifically follow and examine the reaction steps that result in the formation of
metal.

From investigations of excavated quenched submerged arc furnaces, and previous overviews of the
technology and the process steps [1-8] the following idealised reaction zones have been identified (see Fig.
1). Note however that the exact positions of these zones appear to vary with furnace design and operating
practice. The zones do not necessarily follow a simple layered structure as was envisaged in early models of
the process.

Figure 1. Schematic diagram of the reaction zones in submerged arc furnace for
ferrochromium production (principally [8])

Proceedings: Tenth International Ferroalloys Congress; 1 – 4 February 2004

INFACON X: ‘Transformation through Technology’ Cape Town, South Africa
ISBN: 0-9584663-5-1 Produced by: Document Transformation Technologies
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1.1 Upper furnace Zone 1 Loose charge
The loose charge zone extends from the charge layer down to near to the tip of the electrode.

The following reactions occur in this zone;

• Preheating of the charge.
• Decomposition of limestone fluxes e.g. CaCO3, and other minerals.
• Gasification of carbon; reaction with air and CO2.
• Gaseous reduction of chromite ore and partial metallisation of iron and chromium oxides.

According to Ringdalen [8] “most of the volume in the submerged arc furnace is loosely sintered burden”.
The average retention time in this zone was estimated to be 24 hours, but only approximately 20% of
reduction of the charge takes place in this loose charge zone; no liquid slag is formed.

Yamagishi [2] demonstrated, through the use of alumina tracers, that the burden material descended in a V-
shaped distribution, and rate of descent reaches a maximum at positions between the furnace walls and the
electrodes and between the electrodes themselves.

Temperature profiles and excess gas pressures in this zone were measured by Ostrovskii [4] and quoted by
Kossyrev and Olsen [7]. These data show that the 1600oC isotherm was achieved only close to the electrode
tips, and that above 1673K the gas pressure rises rapidly, the later temperature corresponding to the onset of
slag formation.

1.2 Lower furnace (Zones 2-6)

1.2.1 The reactions occurring in the lower furnace involve;

Slag formation
Dissolution of chromite in slag
Reduction of metal from the slag phase and metal alloy formation
Alloy/slag separation

1.2.2 Sidewall slag/metal/ore/coke (Zone 2)

Banks of rigid, partially fused/partly-reduced material are formed in zone 2 adjacent to the furnace walls.
These banks are thickest at distances furthest from the electrodes.

1.2.3 Sidewall/Slag/metal (Zone 3)

The material below zone 2 contains mixtures of slag and metal.

1.2.4 Beneath the electrodes (Zone 4)

There is some uncertainty in the literature about the material present immediately under the electrode tips.
These zones do not connect with the similar zones under the other electrodes (A, B, C). Yamagishi [2]
indicates the presence of a void may have been due to contraction of the bed during cooling of the furnace;
Wedepohl and Barcza [5] report slag and coke under two electrodes but mainly slag under the third
electrode; Ringdalen [8] indicates the presence of a coke bed, containing a mixture of melted gangue
minerals, fluxes and MgO and Al2O3 liberated from the chromite during reduction. Due to the formation of
partially solidified charge materials around the electrodes (zones 2 and 3) the active slag reduction zone is
restricted in size. The residence time in the high temperature smelting zone, defined here as the coke bed
(zone 4), is relatively short, possibly of the order of 30-40min.

1.2.5 Slag (Zone 5)

Yamagishi [2] and Wedepohl and Barcza [5] found a distinctive slag layer; Ringdalen [8] however, report
that “no distinctive slag layer was found”. Yamagishi [2] and Kossyrev and Olsen [7] both report the
presence of a large region of “unmolten partly reacted lumpy ore” between the slag and metal.

1.2.6 Metal (Zone 6)

All previous studies show the formation of a distinct liquid metal alloy layer at the base of the furnace.

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2. REACTION STEPS

The chromite charge to the furnace is principally in the form of lump ore and /or pellets. The lump ore
material consists of chromite grains surrounded by solidified host rock (Fig. 2). Pellets are made from
chromite concentrates that have been agglomerated and pre-treated to form spherical particles (Fig. 3). The
grain size and microstructures of the chromites are variable from dense rounded grains in the lump to highly
fractured acicular grains in the pellets. The particle size ranges of lump, pellet and coke are controlled to
maximise bed permeability. Chromite grains are not necessarily uniform in composition since there are
variations between ore bodies, and even between and within ore seams. The chromite forms part of the spinel
crystal family, having the general formula (Fe2+, Mg2+)O.(Al3+,Cr3+,Fe3+)2O3.

As the charge descends and passes through the reaction zones various reactions occur during metal alloy
formation. These reaction steps are now reviewed in more detail.

Figure 2. Micrograph illustrating the typical Figure 3. Micrograph illustrating the

structure of South African lump chromite ore. structure of a chromite pellet.

Figure 4. Micrograph of South African lump Figure 5. Micrograph of South African lump
chromite reduced 1473K, 4 h, CO gas. chromite reduced 1673K, 0.5 h, CO gas.

2.1 Gaseous reduction of chromite

The mechanisms and kinetics of gaseous reduction of solid South African chromites ore have been studied
by a number of workers [9-29]. There appears to be general agreement that in the loose charge (zone 1) iron
is preferentially reduced from the solid chromite grains by reaction with carbon monoxide gas produced in
the lower furnace.

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The rate limiting reaction mechanism during the gaseous reduction of dense chromite grains is the ionic
diffusion of metal species in the solid spinel phase. Soykan et al [19] proposed that the reduction of chromite
occurs by the following sequence of reactions;
a) “Initially, Fe3+ and Fe2+ at the surface of the chromite particle are reduced to the metallic state. This is
followed immediately by the reduction of Cr3+ ions to the divalent state.
b) Cr2+ ions diffusing toward the centre of the particle reduce the Fe3+ ions in the spinel under the surface of
the particle to Fe2+ at the interface between the inner and outer cores. Fe2+ ions diffuse towards the
surface, where they are reduced to metallic iron.
c) After the iron has been completely reduced, Cr3+ and any Cr2+ that is present are reduced to the metallic
state, leaving an iron- and chromium- free spinel, MgAl2O4”.

The partially altered chromite contains a dispersion of fine iron/chromium metal alloy particles. The solid
alloy, formed in the early stage of reduction as the charge descends and is heated through zone 1, is low in
chromium. As the reaction time and temperature increases, the chromium concentration in the alloy
increases. In later stages of reduction chromium - iron carbides are observed to form [17,19].

The thermodynamics of reduction behaviour of iron-chromium ore in the presence of carbon are discussed
by Hino et al [24]. These authors predict the stable phase assemblages as function of temperature and
CO/CO2 gas mixtures for Fe-Mg-Cr and Fe-Mg-Cr-Al spinels in the absence of fluxes. As reduction
proceeds at progressively higher temperatures the sequence of stable phases expected at carbon saturation
with South African ores is:

1390K, solid Fe + (Fe,Mg)O.(Cr,Al)2O3;

1470K, liquid Fe + (Fe,Mg)O.(Cr,Al)2O3;
1670K, liquid Fe + (Cr,Fe)7C3 + MgO.(Cr,Al)2O3;
1850K, liquid Fe + Cr3C2 + MgO.Al2O3.

In general the reaction proceeds topochemically, from the surface of the particle in the case of dense ore or
from the surface of individual grains for porous materials. In cross section, this compositional variation
within a grain is seen in the form of a core of primary spinel surrounded by continuous shell of secondary
spinel of variable composition. The composition and thickness of the shell varies with slag composition,
temperature, oxygen potential and reaction time (Fig. 4). The Fe-Cr alloy forms initially on the outer surfaces
of the grains or along microcracks.

The rate and extent of reduction of the chromite ore is dependent on the chemical composition of the
chromite, grain and particle size, porosity, and temperature history in pre-treatment and in the furnace [23].
Chromite ores are not uniform in composition; they vary widely with source of material particularly in iron
concentration. The relationship between the degree of reduction and the chromium reduction therefore
depends on the initial composition.

Since the rate limiting reaction mechanism involves solid-state diffusion, diffusion path length is a critical
factor determining reaction rate. The ionic flux to the gas/solid interface is inversely proportional to the
distance, so that reduction rate is enhanced with decreasing particle and grain size. Even cracks and sub-
grain boundaries within the grains enhance the rates of reduction of individual chromite grains. The
reduction rates of individual grains in pelletised materials are significantly faster than in lump material
because of the smaller grain sizes and the higher porosities of the pellets.

The rate of reduction of the chromite can also be influenced by the composition and proportion of matrix
material in the particles, since this material fuses and eventually melts as the charge descends through the
furnace. The formation of the liquid phase can have multiple effects. If there is a high proportion of matrix
material the porosity of the ore, and consequently the ease of reducing gas penetration into the particle, may
be diminished (Fig.5). On the other hand the partially reduced spinel may react with and dissolve in the
molten slag phase, decreasing the effective particle size and influencing the temperature at which the grains
in the chromite particles become dispersed in the bulk slag.

4
The preprocessing of the run-of-mine ore to produce concentrates and pellets is clearly targeted at enhancing
the reduction characteristics of the ore to ensure maximum reduction takes place through gaseous reduction.
The effects of preprocessing on the kinetics of reduction have been reported in a number of studies [24-29].

2.2 Release of iron/chromium alloy, carbide and chromium into slag as a result of
the dissolution of spinel
Ringdalen [8] indicates that most of the reduction takes place in the coke bed situated below the electrode
tips. In the particular furnace investigated the coke bed was estimated to be 0.8-1.0m high and 1.5m wide
(the width of the electrode), and to have an average temperature up to 1973K. Based on the furnace
geometry, she estimated that the residence time in this area of the furnace (zone 4) to be 20-30 min. The slag
produced following ferrochromium smelting contains significant quantities of chromium in the form of
partially altered chromite (PAC) and entrained alloy. According to the results of the Ringdalen [8] study,
there is a great variation in the compositions of the chromite and metal particles dispersed in the slag. The
variations are attributed to mixing in the loose charge due to high gas flows in zone 1. This variation in
degrees of reduction of the chromite entering the reduction zone may equally be explained by the non-
uniform movement of the loose charge material as indicated by Yamagishi [2]. Material close to the furnace
walls and the electrodes would have longer residence times in zone 1 than material midway between these
restrictions. This problem of non-uniform reduction and the risk of insufficient prereduction of chromite
would be exacerbated by the restricted cross section formed by the presence of the partially fused material in
zone 2 in the furnace. Although the pre-reduction steps result in the reduction of metallic iron from the
chromite, the removal of the alloy and the remaining chromium from chromite ore and the slag to form alloy
product involves a series of quite different chemical reaction steps and mechanisms.

As indicated in the previous section it has been shown that alloy and carbide are formed during gaseous
reduction. It has been shown that a rim of secondary spinel, approaching the composition MgAl2O4, is
formed on the surface of the particles, physically separating the primary chrome-containing phase from the
reducing atmosphere and the slag. This secondary spinel must be dissolved in the slag in order to physically
release alloy/carbide that has already been formed during pre-reduction and to release the remaining
chemically bound iron and chromium in the primary chromite. It has been shown by a number of
investigators [30-32,34] that the addition of silica and the resulting formation of liquid slag can dissolve
these partially altered chromites (PACs) and enhance the rate of reduction of chromium from the ore. A
micrograph showing partially reduced chromite in slag is shown in Figure 6.

The extent to which spinel is dissolved in slag is dependent on:

• Temperature
• Slag composition
• Slag volume
• Oxygen partial pressure
• Residence time in the high temperature zone

The effects of these process variables on spinel dissolution have been investigated in [30-36].

Demir and Eric [33,36] examined the dissolution of sintered chromite ore rods (15mm diam. x 19mm long)
in a range of slag compositions at (1873K) under reducing conditions. The progress of the dissolution was
followed by bulk chemical analysis of the slag composition as a function of time; no metallographic
examination is reported. The authors report in almost all experiments “ the rapid introduction of chromium
from the cylinder into the slag phase within the first 15 min.”.

Ringdalen [8] examined the reduction of (90% -300 µm) Turkish fine chromites with coke, with quartz and
bauxite flux additions. The target slag at full reduction was 40%MgO-26%Al2O3-34%SiO2 having a liquidus
temperature of 1973K. Electron microprobe X–ray analysis of the samples demonstrated an initial increase in
chromium concentration in the bulk slag phase up to at least 8wt%oCr2O3. The chromium concentration of
the bulk slag was subsequently progressively lowered through chemical reduction to less than 0.5wt% Cr2O3
in less than 50 min. The initial dissolution of chromium into the slag phase is clearly rapid compared to the
reduction reaction. In spite of this initial rapid dissolution of the chromite, the spinel particles were not
completely dissolved even after 5 hours reduction. Ringdalen [8] also observed that the presence of excess
carbon, generating lower oxygen partial pressures, results in faster reduction of Turkish fines chromite.

5
 Figure 6. Ferrochromium smelting slag at 1873K Figure 7. Ferrochromium smelting slag “slow
containing undissolved, partially altered chromite cooled” from the furnace showing the precipitation
(PAC). of secondary spinel.

Phase equilibrium studies relevant to chromium smelting are listed in references [37-62]. Although the
dissolution of chromium oxide under oxidising conditions is limited (Cr2O3-MgO-SiO2 in air, [56], Cr2O3-
SiO2-Al2O3 in air, Degterov and Pelton [54]), under reducing conditions, approaching chromium metal
saturation the solubility of chromium oxide in slag is greatly enhanced. (CrOx-MgO-SiO2 Cr metal
saturation, Slag Atlas [56]; CrOx-CaO-SiO2, Muan [50]; CrOx-CaO-MgO-Al2O3-SiO2, Morita et al [52];
CrOx-MgO-Al2O3-SiO2, Kossyrev et al [55]; CrOx-SiO2-Al2O3, Degterov and Pelton [54]).

For slags from which chromium has been reduced, the slag system is represented most simply by the ternary
system MgO-Al2O3-SiO2 [56]. A feature of this diagram is the primary phase field of the refractory spinel
MgO.Al2O3. Within this primary phase field the liquidus temperature of 1873K appears to be not greatly
dependent on the MgO/Al2O3 ratio in the slag. Approximately 40wt% SiO2 in this ternary would ensure that
the slag is completely liquid at 1873K for slags with MgO/Al2O3 mol ratios of unity. Yonggao [57] reports
the melting points of MgO-Al2O3-SiO2 slags between 30-40wt% SiO2 and MgO/Al2O3 = 0.8-2.8 however no
information is provided on the technique used to determine these values.

Most industrial slags also contain lime flux of various proportions. The liquidus surfaces for the system CaO-
MgO-Al2O3-SiO2 quoted in “Slag Atlas” [56] and “Phase Diagrams for Ceramists” [42] are principally
derived from the work of Osborn et al. [38]. Liquidus temperatures in the system Cr2O3-CaO-MgO-Al2O3-
SiO2 in air have been reported for selected sections, (Berry et al. [38]; El-Shahat and White [43-45]; Biggar
and O’Hara [46]; Biggar [47,48]; Onuma and Tohara [49]; Segadaes and Brett [51]. These studies are
principally focused on composition areas and reactions occurring in the production of chrome-magnesite
refractories.

In submerged arc smelting practice, if complete dissolution of the chromite grains does not take place in the
hot zone (Zone 4) then it is unlikely that significant further reduction will occur in the furnace. The
argument here is that as the slag moves away from the electrodes there is a decrease in slag temperature. The
slag tapping temperatures (approximately 1873K) are below those in the coke bed. If the slag is already
saturated with the spinel MgO.Al2O3 in the coke bed then cooling will lead to further precipitation on the
existing solid surfaces, which act as heterogeneous nucleation sites for the precipitate phase. The formation
of these secondary spinels on the surfaces of the PACs and the partial crystallisation of the melt is illustrated
in the micrograph of the tapped slag shown in Figure 7.

As indicated above the solubility of chromium oxide in slag increases with decreasing oxygen partial
pressure. Chromium can exist in slag solution as Cr6+, Cr3+and as Cr2+[58-62]. Xiao et al. [62] recently
reviewed the data available on the Cr3+/ Cr2+ ratios in molten CrOx-CaO-SiO2 slags for a range of slag
compositions and oxygen partial pressures. Xiao and Holappa [59] has used a regular solution
thermodynamic model to estimate the CrO and Cr2O3 activities in a range of slag compositions at 1873K.

6
2.3 Reduction of chromium from the slag by solid carbon
Once in solution in the slag the chromium can be reduced by carbon to form metal alloy or carbide [63-78].

The effects of silica on the kinetics of reduction of friable Zimbabwean chromite ore (65% - 600 µm) with
fine coke (-500 µm) at temperatures between 1623 and 2023K have been investigated by Taneka and
Robertson [64]. The extent of reaction was followed by measuring the total gas volume produced by the
reaction as a function of time. At reaction temperatures of 1923 and 2023K, complete reduction was
achieved within ten minutes. Residual chromium in the slag was quoted as 0.3 to 2.7wt% Cr2O3. Silica
reduction from the slag was also observed to occur at these high temperatures.

Fukagawa and Shimoda [67] reduced sintered fluxed South African chrome ore in graphite crucibles at
1923K. A range of CaO/SiO2 mixtures, which were used as fluxes, from 0.6 to 1.63 were investigated. The
reaction rates were calculated based on observations of slag erosion of the carbon crucibles following the
experiments. On this basis the rates at CaO/SiO2 = 0.6 appeared to be low, but as the authors point out this
also corresponded to foaming of the slag during reaction. Slag foaming could be interpreted as indicative of a
vigorous reaction; the foaming may also be due to the higher viscosities of these slags. The samples reduced
using flux containing CaO/SiO2 = 1.63, and MgO for CaO/SiO2 = 1.1, gave significantly lower reaction rates
particularly at greater extents of reaction.

Shimoo et al [68,69] investigated the reduction of iron-free CaO-SiO2-Cr2O3 and CaO-Al2O3-Cr2O3 slags
with graphite between 1773 and 1973K. In these cases, chromium carbides have been observed to form on
the surfaces of carbon particles. They observed that the rate of reduction increased significantly with the
formation of carbide product layer on the carbon surface. The formation of carbide also resulted in the
increased wettability of the solid surface by the slag. The reduction rate varied significantly with
composition of the CaO-SiO2 slag.

The reduction of (Fe,Mg)O.Cr2O3 spinels in CaO-SiO2 slags was also studied at 1873K by Shimoo et al.
[71]. The reduction of iron from the spinel was found to precede the reduction of the chromium. The
reduction of chromium from the binary CaO - SiO2 slags was found to be relatively slow as a result of poor
slag/C contact. The presence of MgO and/or Al2O3 considerably improved the wettability of the slag and the
reaction rate.

Pei and Wijk [72] report the reduction of chromium oxides from iron-free CaO-MgO-Al2O3-SiO2 slags using
14mm ID graphite crucibles. Initial reactions result in the reduction of Cr3+ in the slag to Cr2+; further
reduction resulted in the formation of chromium carbide. Below 1798K solid Cr3C2 is observed to form at the
slag/carbon interface, above 1823K the reduction product is liquid Cr-C alloy. Reduction of initially 1.2wt%
Cr2O3 to less than 0.2wt% Cr2O3 was achieved within 10 minutes at 1923K, and it was argued that the rate
was limited by mass transfer in the slag phase.

The effects of silica addition on the kinetics of reduction of Greek chromites at 1573 and 1673K using
graphite powders have been studied by Lekatou and Walker [75]. Chrome metallisation in these tests did not
exceed 80% and no systematic study was carried out on the effects of slag chemistry.

Gornerup and Lahiri [76] studied the reduction of chromium from CaO/SiO2 slags in graphite crucibles at
temperatures from 1723-1973K. The synthetic slags contained initially 5wt% chromium in solution, and
CaO/SiO2 ratios from 0.8 to 2.0 were investigated and the liquidus temperatures were determined to be less
than 1673K. At temperatures above the melting temperature of metallic iron, complete reduction of iron and
chromium from the slag was reported within 20 minutes of the start of the experiment. Iron and chromium
concentration profiles in the slag phase adjacent to the crucible wall, determined by electron probe X-ray
microanalysis, indicated that the rates were limited by slag phase mass transfer.

Kucukkaragoz et al. [77] and Vadar and Eric [78] investigated the reduction of South African chromite ores
entrapped in slag in an inductively heated graphite crucible. Dip samples of slag were taken during reaction
and bulk chemical analysis performed. The effects of slag composition on rate of reduction are reported for a
range of slag chemistries at 1873K.

7
The effect of carbon type on the rate of reduction of chromium from slags does not appear to have been
systematically studied. Dijs and Smith [65] examined the use of carbons and coke up to 1773K; they found
that carbons with higher CO2 reactivity gave faster rates of reduction of the slag.

Figure 8. Micrograph showing the interface Figure 9. Micrograph showing the interface
between ferrochomium smelting slag and graphite. between ferrochomium smelting slag, coke and
alloy.

2.4 Reduction of chromium from the spinel by carbon in molten alloy

Demir and Eric [81]; Uslu and Eric [82]; Eric [85] investigated the reduction of solid chromite by carbon in
Fe-Cr-C alloys using a rotating cylinder technique. The extent of reaction was followed by measurement of
changes in the alloy composition with reaction time. Experiments were carried out between 1773 and 1953K
and carbon concentrations of 4, 5 and 7wt%. Examination of the partially reduced samples after 30 minutes
reduction revealed the formation of a (Cr,Fe)7C3 carbide layer that covered the reaction interface. The
presence of this solid product layer leads to a significant decrease in the rate of reduction of the spinel. The
overall rates of carbon decrease in the alloy were reported but these data were not translated into apparent
interfacial reaction rates.

2.5 Reduction of chromium in solution in slag by carbon in molten alloy

Yokoyama et al. [89] reported a series of experiments examining the reduction of chromite ore with Fe-Si-C
melts in graphite crucibles at temperatures between 1743-1903K. The yield of chromium was increased with
the use of high lime fluxes, which were used to dissolve the South African chromite. The reaction was
followed over the reaction time by chemical analysis of slag samples. From results indicating variations in
rate with slag chemistry and the continued presence of undissolved chromite it was concluded that the rates
were limited by mass transport in the slag phase under these conditions.

Pei and Wijk [89,90] studied the reduction of Zimbabwean chromite ores in Fe-C melts in graphite crucibles
at 1903K. The chromite was dissolved in CaO-SiO2 slags but the effects of MgO and Al2O3 additions were
also examined. In the case of CaO-SiO2 slags, the chromium oxide concentration of the slag was observed to
initially increase, reaching a maximum value of approximately 3wt% within 10 minutes; complete
dissolution and reduction of chromium oxide from the slag was achieved within 20 minutes. The addition of
MgO and Al2O3 resulted in significant decreases in the maximum chromium oxide concentration observed in
the slag and greatly reduced overall reduction rates.

The reduction of Zimbabwean chromite ores by Fe-C melts was also studied by Tsomondo et al [93]. The
total chromium concentration in the CaO-SiO2 based slag was monitored as a function of reaction time at
temperatures in the range at 1853-1913K. The reduction kinetics were described by a first order rate equation
with respect to the chromium concentration in the slag. The initial reaction rates were observed to be rapid in
all cases, however, the residual chromium in the slag was found to increase with decreasing basicity from 1.5
to 0.5.

8
Following earlier studies of the reduction of chromium from slags in graphite crucibles Gornerup and Lahiri
[94, 95] added Fe and Fe-C powders to the slags at 1873K; the result was a dramatic increase in reaction rate
accompanied by severe foaming.

Nakasuga et al. [96] studied the rate of reduction of chromium from Cr2O3-CaO-MgO-SiO2-Al2O3-CaF2
slags with carbon in molten Fe-C alloys at 1773 and 1873K. The reduction rate was such that “almost all of
the Cr2O3 was reduced from the slag within 10 minutes”. The rate of reduction was found to increase with
increasing CaF2 addition; this effect is attributed to the decrease in slag viscosity accompanying these
additions.

It is now widely accepted that the reaction mechanisms between slag and carbon in alloy involves a two-step
process with the formation of a gas film at the slag/alloy interface [87,91,92,94].

Carbon gasification from the alloy

C (in alloy) + CO2 (gas) → 2CO (gas) (1)

Gaseous reduction of the slag

CO (gas) + O (slag) → CO2 (gas) (2)
The so-called gas ferrying mechanism is shown in Fig. 10. It has been established that the chemical rates of
carbon gasification from the alloy surface are at least an order of magnitude greater than from solid carbon
(Sain and Belton, [86]). To retain the alloy as liquid and to ensure an adequate supply of carbon for reaction
(1) the rate of dissolution solid carbon into the alloy should also be rapid. The rates of carbon dissolution in
metal have been shown, to be dependent on carbon type [98].

The relative contributions of gasification via solid carbon and carbon dissolved in alloy to the overall
reactions will depend on the surface areas of carbon and alloy at the carbon/slag interface, CO2 reactivity and
carbon dissolution rates in alloy [97].

The reaction mechanisms at the carbon surface can also influence the gas evolution from these surfaces. The
slag phase generally does not wet the carbon surface [Fig.8], but it has been observed to wet the molten alloy
[Fig.5 and 6]. If the gasification occurs between solid carbon and the gas phase the product gas will
accumulate into relatively large gas bubbles before becoming detached from the carbon. Gasification at the
metal surface, although faster, has been shown [97] to produce relatively fine (1mm diameter) bubbles,
which have a tendency to form stable slag foams.

The selection of the optimum carbon type for use in submerged arc processes remains an area of interest for
commercial practice.

Figure 10. Summary of reaction mechanisms occurring in the lower furnace

during submerged arc smelting of ferrochromium.

9
 Temperature
∼1973K
slag

Temperature
∼1873K

slag

Figure 11. Alternative reaction pathways for reduction of ferrochromium slags with carbon.

3. SUMMARY

As chromite ore moves through the submerged arc furnace during processing it passes through a number of
reaction zones.

In the upper furnace, zone 1, the chromite particulates are present as “loose charge” and product gas from the
lower furnace consisting of principally CO and CO2 passes through this packed bed. Reactions between the
gases and the solid chromite result in the partial reduction of the chromite and the formation of iron and
chromium alloy, and in some cases metal carbides.

In the lower furnace, zones 2-6, a series of reaction steps take place involving the slag phase (Fig. 11):
• Dissolution of chromite spinel in slag
• Reduction of the slag phase to form alloy
• Alloy/slag separation

Although the overall reaction is described by the removal of oxygen by solid carbon, this reaction can take
place through a number of pathways involving; carbon monoxide formation from solid carbon or carbon
dissolved in alloy; reaction of CO gas with slag; metal ion diffusion in the slag phase.

Each of these mechanisms contributes to the overall recovery of chromium as alloy. Optimisation of the
process to enhance the rates and extent to which these reactions proceed, and to maximise recovery,
production rate and energy efficiency is assisted by improved understanding of the various reactions and
reaction mechanisms operative in the process, and by taking action through feed selection and preparation,
and adjustment of process conditions.

10
4. REFERENCES

Submerged arc furnaces

[1] Urquhart R.C., “A study of the production of high carbon ferrochromium in the submerged arc furnace”,
PhD thesis Univ. of Witswatersrand, 1972.
[2] Yamagishi K, Endo K and Saga J., “A comprehensive analysis of the furnace interior for high carbon
ferrochromium”, INFACON 1, Johannesburg, South Africa, 1974, pp. 143-178.
[3] Ostrovskii Ya. I., Vorob’ev V.P. and Kozhevnikov G.N., “Gas stream in the bath of a closed electric
furnace smelting of carbon-containing ferrochromium”, Stal, 1976, no.7, pp.618-620.
[4] Ostrovskii Ya. I., PhD dissertation, “Investigation of some particularities of technology of melting
carbon ferrochromium”, Inst. Metall., Sverdlovsk, USSR, 1976.
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