http://dx.doi.org/10.

17159/2411-9717/2019/v119n2a13

Recycling pre-oxidized chromite fines in

the oxidative sintered pellet production
process
by S.P. du Preez*, J.P. Beukes*, D. Paktunc†, P.G. van Zyl*,
and A. Jordaan*

According to this review, FeCr is principally

produced in (i) conventional open/semi-closed
 
 submerged arc furnaces (SAFs) that are
The chromium (Cr) content of stainless steel originates from recycled scrap mainly fed with lumpy (typically 6–150 mm)
and/or ferrochrome (FeCr), which is produced mainly by the carbothermic chromite ore, fluxes. and reductants, (ii)
reduction of chromite ore. The oxidative sintered pellet production process closed SAFs that are fed with oxidative
is one of the most widely applied FeCr processes. The supplier of this sintered chromite pellets, as well as lumpy
technology specifies that recycling of chromite-containing dust collected reductants and fluxes, (iii) closed SAFs fed
from the pellet sintering off-gas and fines screened out from the sintered with prereduced chromite pellets, as well as
pellets (collectively referred to as pre-oxidized chromite fines) should be
lumpy reductants and fluxes, and (iv) closed
limited to a maximum of 4 wt% of the total pellet composition. However,
direct current (DC) arc furnaces fed with fine
the results presented in this paper suggest that recycling of such fines up
to a limit of 32 wt% of the total pellet composition may improve the (typically
6 mm) chromite ore, fluxes, and
compressive and abrasion strengths of the cured pellet. In addition, reductants. Of particular interest for the present
electron microprobe and quantitative X-ray diffraction (XRD) analyses paper is the oxidative sintered pellet process,
demonstrate that chromite grains present in the pre-oxidized chromite which is commercially known as the Outotec
fines consist, at least partially, of crystalline phases/compounds that will steel belt sintering process (Outotec, 2017).
improve the metallurgical efficiency and specific electricity consumption Various authors have previously described
(i.e. MWh/ton FeCr produced) of the smelting process. the oxidative sintered pellet production process
   (Riekkola-Vanhanen, 1999; Beukes, Dawson,
Chromite, ferrochrome, ferrochromium, pre-oxidation, oxidative sintering, and van Zyl, 2010; Basson and Daavittila,
recycling. 2013). Chromite fines (typically
1mm) are
wet milled together with a small percentage of
a carbonaceous material that serves as an
energy source during sintering. The grain size
specification that must be obtained during
milling is typically a d80 of 74 μm (80%

 
 passing size of 74 μm). Ceramic filters are
Stainless steel is a vital modern-day alloy that used to dewater the milled slurry to a moisture
is well-known for its corrosion resistance, content of below 9%. A fine clay binder
which is mainly due to the inclusion of (usually refined bentonite) is then mixed into
chromium (Cr) (ICDA, 2013). Stainless steel is the moist filter cake with a high-intensity
mostly produced from recycled scrap and mixer, and the moist mixture is pelletized in a
ferrochrome (FeCr), a relatively crude alloy of pelletizing drum. The newly formed pellets are
Cr and iron (Fe). FeCr is predominantly screened on a roller screen. Oversized pellets
produced by the carbothermic reduction of are broken down and recycled, together with
chromite, a mineral belonging to the spinel undersized pellets. This leads to fairly
group characterized by the unit formula homogeneously sized green (uncured) pellets
[(Mg,Fe2+)(Al,Cr,Fe3+)2O4] (Haggerty, 1991; with an average diameter of approximately
Paktunc and Cabri, 1995; Tathavakar, Antony, 12 mm. The green pellets are then layered on a
and Jha, 2005). Although Cr can occur in 82
different minerals, chromite is the only source
of new Cr units that can be exploited in
commercial volumes (Motzer and Engineers,
2004). Approximately 95% of mined chromite
is used in the production of various FeCr * Chemical Resource Beneficiation (CRB), North-
grades, of which high-carbon and charge West University, Potchefstroom, South Africa.
† CanmetMINING, Natural Resources Canada,
grade FeCr are the most common (ICDA,
Ottawa, Canada.
2013). © The Southern African Institute of Mining and
Beukes et al., (2017) recently presented a Metallurgy, 2019. ISSN 2225-6253. Paper received
review of FeCr production processes. Dec. 2017; revised paper received Aug. 2018.


   

 

 
 

 207
Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process
perforated steel belt, which carries the pellets through a homogeneous, representative sample, a bulk sample of
multi-compartment sintering furnace. The perforated steel approximately 320 kg was taken by manually collecting
belt is protected against excessive temperatures by a layer of shovel loads of material at various points and various heights
previously sintered pellets below the green pellets. The of the ore stockpile. The bulk sample was then split at the
temperature of the pellet bed gradually increases as it passes laboratory of the FeCr producer three times with a riffle-type
through the sintering furnace, reaching a maximum of sample splitter to yield a sample of approximately 80 kg,
approximately 1400 to 1500°C. Sintered pellets are then which was transported to the laboratories at the Chemical
cooled by air blown through the pellet bed from below. Resource Beneficiation (CRB) unit, North-West University.
Thereafter, the sintered pellets are discharged and screened There, the sample mass required for a specific experiment
to remove < 6 mm material, but screening at a smaller was obtained by splitting the sample further using a vibrating
aperture has also been observed by the authors during plant feeder that fed a rotating tray of containers. Previously,
visits at FeCr producers applying this process. The overall Glastonbury et al., (2015) presented a detailed
process produces porous and mechanically strong pellets characterization of this case study ore, therefore such a
suitable for SAF smelting (Riekkola-Vanhanen, 1999), which characterization is not repeated here. In short, the ore
results in improved SAF stability and metallurgical efficiency, contained 44.19 wt% Cr2O3, 24.68 wt% FeO, 14.71 wt%
as well as lower energy consumption compared with Al2O3, wt% 10.31 MgO, and 2.96 wt% SiO2, and had a Cr/Fe
conventional SAF smelting of lumpy ore (Basson and ratio of 1.58 (Glastonbury et al., 2015). This composition is
Daavittila, 2013). representative of a typical South African metallurgical grade
The suppliers of the steel belt sintering technology chromite ore (Cramer, Basson, and Nelson, 2004). It has to
indicated that chromite-containing dusts collected from the be considered that a substantial fraction of the chromite
pellet sintering scrubber and fines screened out from the smelted outside South Africa originates from South Africa. In
sintered pellets can be re-introduced into the moist material 2012 for instance, 28% of the chromite ore consumed in the
mixture that is pelletized (Basson and Daavittila, 2013). rest of the world originated from South Africa (Kleynhans et
However, it is specified that the addition must be limited to a al., 2016). Therefore, the results generated from the case
maximum of 4 wt% of the total pellet composition, since this study ore are of international relevance.
material is believed to adversely affect pellet quality (Basson A sample of chromite fines screened out from industrially
and Daavittila, 2013). The fundamental reasoning behind produced sintered pellets was obtained from a large FeCr
this limitation is not stated in the public peer-reviewed producer in South Africa that utilizes the oxidative sintered
domain. A recent personal communication indicated that pellet production process. In this paper, this material is
specifically, pellet strength deteriorates with increasing referred to as ‘pre-oxidized chromite’. This material was
content of recycled pre-oxidized fines (Päätalo, 2018). This sampled in a similar manner as the ore. Refined bentonite
can be countered by increasing the clay binder and carbon (binder) and coke fines (carbon fuel source), which were
contents in the green pellets. However, an increased carbon used to produce oxidative sintered pellets at the
content could lead to higher sintering temperatures, which aforementioned FeCr producer, were also obtained.
may result in a shorter operational life of the steel sintering Kleynhans et al., (2012, 2017) previously presented full
belt (Päätalo, 2018). characterizations of the bentonite and coke fines (sample Co5
The authors were approached by a FeCr producer at in Kleynhans et al., 2017), therefore this information is not
which the generation of pre-oxidized fines, originating from repeated here.
the sintering scrubber and screening of the sintered pellets,
exceeds the 4 wt% limitation. This has resulted in the     
accumulation of pre-oxidized fine chromite stockpiles. Pre- Material for pelletization experiments was prepared by dry
oxidized chromite requires less energy to metallize compared milling a 50 g mixture, consisting of 1.5 wt% coke, with
to normal chromite (Kapure et al., 2010). Furthermore, the chromite the balance, for 2 minutes in a Siebtechnik
reduction of oxidative sintered pellets requires less energy laboratory disc mill. Prior to milling, all materials were dried
(Zhao and Hayes, 2010) and pre-oxidation of chromite fines in an oven overnight at 75°C to enable accurate and
significantly improves prereduction (solid-state reduction) of repeatable batching of the mixtures. A tungsten carbide
chromite (Kleynhans et al., 2016, 2017). Considering these grinding chamber was used to avoid possible Fe
energy-related benefits, the authors believe that all pre- contamination. This milling procedure yielded a particle size
oxidized fine chromite should be recycled on-site at FeCr distribution with a d80 of 75 μm, which is similar to the
producers. With this in mind, the possible recycling of pre- industrial particle size specification, i.e. d80 of 74 μm (Basson
oxidized chromite fines into oxidative sintered pellets beyond and Daavittila, 2013; Glastonbury et al., 2015). After milling,
the current limitation of 4 wt% pellet composition was refined bentonite was added to obtain a mixture with a
investigated, considering both fundamental and practical composition of 97.52 wt% ore, 1.49 wt% coke, and 0.99 wt%
aspects. bentonite. The pelletization mixture was then vigorously
blended for 15 minutes using a laboratory-scale Eirich-type
478564-1943/9)87.2/1 mixer. As-received pre-oxidized chromite was then added to
the pelletization mixture to obtain mixtures containing 4, 8,
  16, 32, and 64 wt% pre-oxidized chromite. No additional
A metallurgical grade chromite ore sample was received from coke or bentonite was added to these mixtures to compensate
a large FeCr producer in South Africa, which served as the for the addition of pre-oxidized chromite, since this is also
case study ore in this investigation. To obtain a the practice in industry.


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Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process
Green pellets containing the various percentages of pre- ambient atmosphere. The sintering process also took place in
oxidized chromite were generated using a laboratory-scale an ambient gaseous environment and no dwelling time was
disk pelletizer. The laboratory disk pelletizer consisted of a allowed at the maximum temperature, in order to mimic the
600 mm diameter flat steel disk with a 150 mm deep rim. The industrial process as closely as possible.
entire disk and rim were pressed from a single steel plate and
the connection area between the disk and rim was rounded to   
limit material build-up. The pelletizer rotated at a speed of Scanning electron microscopy (SEM) equipped with energy
40 r/min and a constant angle of 60° to the horizontal was dispersive X-ray spectroscopy (EDS) was used to perform
maintained in all experiments. Fine water spray was surface characterization of the sintered pellets in secondary
introduced to the mixture with a handheld spray bottle to electron mode. An FEI Quanta 250 FEG instrument
initiate pellet nucleation, i.e. formation of micro-pellets. incorporating an Oxford X-map EDS system operating at
Thereafter, the micro-pellets were grown by continuously 15 kV and a working distance of 10 mm was used. Pellets
wetting of their surfaces with water spray and introducing were split in half and mounted on aluminium stubs, or were
new, dry feed until the desired pellet diameter was achieved. set in resin and polished with a SS20 Spectrum System
Material build-ups on the bottom, side, and pelletizer corner Grinder polisher before being mounted on the stubs. The
(connecting area between disk and rim) were continuously polished resin-embedded samples were coated with carbon in
loosened with a fit-for-purpose handheld scraper to facilitate an Emscope TB 500 carbon coater prior to SEM analysis.
the inclusion of this material into the pellets. This scraper Resin-embedded polished pellets were imaged in
had a flat edge to remove material build-up from the disk and backscattered electron mode, and un-embedded pellets in
the rim, as well as a rounded point to remove material build- secondary electron mode.
up from the corner. Pellets with a diameter of > 11 and Crystalline phase analysis of bulk samples was performed
< 13 mm were collected by screening. Care was taken to by X-ray diffraction (XRD) using two methods:
ensure a consistent pellet moisture content, with all pellets  A Rigaku D/MAX 2500 rotating-anode powder
used in further experiments containing 5.5 ± 0.7 wt% diffractometer with Cu K
radiation at 50 kV, 260 mA,
moisture. Pellet moisture contents were determined with an a step-scan of 0.02º, and a scan rate at 1/min in 2
ADAM PMB 53 moisture balance. Green pellets were allowed hours from 5 to 70º. Phase identification was
to dry in an ambient atmosphere after collection before performed using JADE v.3.9 with the ICDD and ICSD
oxidative sintering experiments proceeded. diffraction databases
 A Röntgen diffraction system (PW3040/60 X’Pert Pro)
    
and a back-loading preparation method to determine
As previously stated, Basson and Daavittila (2013) indicated
the crystalline phases, and their percentages, present in
that industrially produced oxidative sintered pellets are
size-partitioned samples and milled mixtures.
heated to maximum temperatures of between 1400 and
1500°C. Glastonbury et al., (2015) mimicked the industrially The samples were scanned using X-rays generated by a
applied process on the laboratory scale, with a temperature copper (Cu) K
X-ray tube. Measurements were carried out
profile that attained a maximum temperature of 1400°C. between variable divergence and fixed receiving slits. Phases
However, these authors did not verify how deep into the were identified using X’PertHighscore plus software. Phase
pellets oxidation proceeded. Zhao and Hayes (2010) proved refinement was performed using the Rietveld method (Hill
that only the outer chromite grains of industrially produced and Howard, 1987).
oxidative sintered pellets are partially oxidized, while the Further analysis was undertaken by mounting cross-
chromite grains deeper into the pellets are not oxidized. Heat sectioned polished pellets on glass slides and carbon-coating
transfer to pellets in laboratory conditions, where small them prior to electron microprobe analysis (EMPA). Analysis
amounts of pellets are sintered in batches with very effective was performed using a JEOL JXA-8900 electron microprobe
furnaces, will be significantly superior to that in industrial fitted with five wavelength-dispersive spectrometers at an
furnaces, where very large quantities are treated accelerating voltage of 20 kV and beam current of 26 nA.
continuously. Therefore, rather than blindly selecting a
maximum sintering temperature, or applying the temperature      
 
profile used by Glastonbury et al., (2015), the authors tested The compressive strengths of sintered pellets were
various maximum temperatures. A Lenton Elite camber determined using an Ametek Lloyd Instruments LRXplus
furnace (UK, Model BRF 15/5) with a programmable 5 kN strength tester. NEXYGENPlus material test and data
temperature controller was used for sintering. The analysis software was used to capture and process the
temperature probe of this furnace was situated inside the generated data, as well as to control and monitor all aspects
heating chamber, which ensured that the recorded of the system. The speed of the compression plates was kept
temperature and the actual pellet temperatures correlated to 10 mm/min during compressive strength tests in order to
well. Prior to oxidative sintering, the pellets (in a 99.7% apply an increasing force on the prepared pellets. The
Al2O3 ceramic crucible) and furnace were pre-heated to 100 maximum load to induce pellet breakage was recorded.
and 900°C, respectively. A pellet batch (consisting of 25 Standard deviations were calculated based on 10
pellets) was then placed in the furnace and the temperature experimental repetitions.
was ramped up from 900°C to the designated maximum The abrasion resistance apparatus used in this study was
temperature at a rate of approximately 17°C/min. Once the based on a downscaled version of the European Standard EN
designated maximum temperature was reached, the pellets 15051 rotating drum, as described by Schneider and Jensen
were removed from the furnace and allowed to cool in the (2008). The same drum was utilized in previous studies


   

 

VOLUME 119  

 209
Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process
(Kleynhans et al., 2012, 2016; Neizel et al., 2013; randomly selected from each prepared pellet batch, revealed
Glastonbury et al., 2015). During each experiment, 10 that the outer chromite grains of pellets sintered at < 1200ºC
sintered pellets were abraded at 40 r/min rotational speed for did not indicate signs of oxidation, while oxidation
64 minutes. The pellets were screened at time intervals of. 1, penetrated deep into pellets sintered at > 1200ºC. A sintering
2, 4, 8, 16, 32, and 64 minutes using a sieve with an profile with a maximum temperature of 1200ºC was therefore
aperture of 6.5 mm. This aperture was chosen since < 6 mm applied within the context of this paper, to mimic the
material is generally classified as fines, which have to be industrially applied oxidative sintered pellets process.
limited in SAF feed material (Basson and Daavittila, 2013). Figure 1 presents backscattered electron SEM micrographs
The oversized materials ( 6.5 mm) were weighed and of a cross-sectioned polished pellet containing zero wt%
returned to the drum, together with the fines ( 6.5 mm), for pre-oxidized chromite, which was sintered at a maximum
further abrasion until the full abrasion time, i.e. 64 minutes, temperature of 1200ºC. Oxidation-induced differences
was reached. Standard deviations were calculated based on (alteration being indicated by the lighter greyscale patterns)
three experimental repetitions. were evident between the outer chromite grains and grains
toward the centre of the pellet (Figure 1a). The higher
<81(-71943/9/610(11623 magnification micrograph of the outer chromite grains
(Figure 1b) clearly shows an oxidation-induced altered phase
      that formed on the rim of such grains, while the chromite
  grains toward the pellet centre were unaffected (Figure 1c).
As previously stated, Zhao and Hayes (2010) showed that Similar oxidation-induced phase patterns have been observed
only the outer chromite grains of industrially produced during investigations considering pre-oxidation of chromite
oxidative sintered pellets are partially oxidized, while the prior to direct reduction (Kapure et al., 2010), laboratory
grains deeper into the pellet cores remain unoxidized. oxidative sintering of chromite pellets (Glastonbury et al.,
Therefore, it was critical to establish the maximum 2015), and industrially produced oxidative sintered chromite
temperature for the proposed laboratory sintering profile (see pellets (Zhao and Hayes, 2010).
Pellet oxidative sintering section). Consequently, batches of
pellets were cured with sintering profiles that had maximum    
temperatures from 1000 to 1500ºC. SEM examination of In order to gain insight into the recycling of pre-oxidized
three cross-sectioned, polished sintered pellets, which were chromite fines, it is vital to understand the mechanism(s) at

#6*(58940
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*54631943/9*54631972'45/97.890837589"4!9.8189/6++858308194589%877859188396397.89.6*.859)4*36+604762396)4*8192+97.892(78590.52)6789*546319"%!943/9*54631
72'45/97.8908375892+97.89,8--879"0!


210  

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Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process

Table I
 9"'7!92+9/6++85837954639-2047623943/954639458419419'8--9419*#8943/95#8954762192+97.8
75431+25)476239,52/(0719"0.52)678943/9  ,.418!96394958,581837476891637858/9,8--879")4&6)()916378563*
78),8547(5892+9 !9023746363*9329,58$2&6/68/90.52)67896&97299434-1819'8589023/(078/963916)6-45
-20476231943/94584192+9%87'8839+2(5972986*.79,45760-819'67.97.894854*81943/91743/45/9/86476231963/60478/

54639999999999999546394584 '7 9547621

-2047623 5  -  #8 #8  * 6 
  3 6 * 5
#8 #8

Centre Interior 47.25 15.78 19.77 6.13 9.90 0.70 0.36 0.23 0.12 0.30 1.64
(chromite) ±0.77 ±0.71 ±0.58 ±1.26 ±0.33 ±0.08 ±0.03 ±0.02 ±0.01
Outer Interior 48.49 15.39 15.39 6.75 12.65 0.72 0.36 0.32 0.13 0.46 1.99
±0.76 ±0.92 ±1.12 ±1.02 ±0.69 ±0.06 ±0.03 ±0.05 ±0.02
Outer Rim (M2O3 48.30 16.47 0.21 33.15 0.31 0.79 0.41 0.01 0.01 0.01 1.42
layer phase) ±1.06 ±1.65 ±0.15 ±1.67 ±0.09 ±0.07 ±0.03 ±0.01 ±0.01

play during the oxidative sintered pellet production process. enrichment at the expense of Fe2+ in grains at the outer layer.
Oxidation-induced alteration, which is indicated by lighter Fe2+ occupies the tetrahedral sites in normal (untreated)
greyscale patterns in the SEM micrographs in Figure 1b, was chromite spinel. High-temperature oxidative treatment of
evident on the rims of the outer chromite grains of sintered chromite caused Fe2+ to oxidize and diffuse towards the grain
pellets containing no pre-oxidized chromite. EMPA was rim, generating tetrahedral site vacancies within the particle
subsequently used to determine the chemical compositions of interior. Vacancy formation occurs according to the following
the transformation products. However, access to the EMPA reaction (Lindsley, 1991; Tathavakar, Antony, and Jha.,
was limited, therefore only one pellet, sintered according to 2005)
the optimum sintering profile, was analysed. SEM
micrographs of all three of the randomly selected pellets from [1]
the batch sintered at 1200ºC indicated the same phase
transformations at the rim of the pellets (see Mimicking the where O2-0 represents oxygen anions in the cubic closed
industrial applied oxidative sintering process section), which packed lattice, Vcat is the cation vacancies, and h a ‘hole’,
proved that the randomly selected pellet analysed with EMPA respectively. Vcat + 2h collectively represent mobile point
was representative. The results of the EMPA are shown in defects, from which mass transfer occurs. These tetrahedral
Table I. The areas analysed are indicated as ‘grain location’ vacancies were filled by Mg2+ (originating from the particle
and ‘grain area’, with ‘location’ referring to the position of rim) via a Mg-Fe exchange reaction, which resulted in the
the chromite grain within the pellet (i.e. centre or outer observed 0.31 wt% MgO content at the grain rim in the pellet
grains), and ‘grain area’ referring to the zone within a outer layer.
specific grain (i.e. interior or rim of a specific grain, which is The Fe2+ that migrated to the grain rim in the pellet outer
also indicated in Figure 1b). The Cr/Fe and Mg/Fe elemental layer was subsequently oxidized to Fe3+, or alternatively the
ratios, with Fe = Fe2+ + Fe3+, as determined by EMPA, are Fe2+ was oxidized to Fe3+ which then migrated to the surface
also presented in Table I. – currently it is impossible to say with certainty which occurs
As is evident from Table I, the interiors of grains at the first. The generalized oxidative spinel phase decomposition is
centre and outer layer of the pellets had appreciably different described by Equation [2] (Alper, 1970; Tathavakar, Antony,
MgO and FeO contents, whereas no appreciable differences and Jha, 2005)
between trivalent cations (primarily Cr3+, Al3+, and Fe3+,
indicated as Cr2O3, Al2O3, and Fe2O3, respectively) occupying [2]
the octahedral sites in chromite were observed. In contrast,
relatively large differences in FeO, Fe2O3, and MgO contents The products of complete oxidative decomposition of
were evident for grain interiors and rims located in the outer chromite (Mg,Fe)[Al,Cr,Fe]2O4 at elevated temperatures are
layer of pellets. free oxides of the various species, as indicated by Equation
Grain interiors in the centre of pellets had an MgO [2]. However, in this study complete oxidative decomposition
content of 9.90 wt%, compared to 12.65 wt% at the outer was not the intention, nor was it achieved. The products of
layer. The FeO content of grain interiors at the centre and chromite oxidation are strongly dependent on temperature,
outer layer of pellets were 19.77 and 15.93 wt%, respectively. oxygen partial pressure, and the chemical composition of the
Consequently, the Mg/Fe ratios for grain interiors at the pellet chromite. In the presence of oxygen, Fe2+ will be oxidized to
outer layer were higher (0.46) than for grains at the pellet Fe3+ at sufficiently high temperatures. This explains the
centre (0.30). The Mg/Fe ratio difference of grain interiors as decrease in FeO content of 15.39% to 0.21% and increase in
a function of location within the pellet was indicative of Mg2+ Fe2O3 content of 6.75 to 33.15% from the grain interior to


   

 

VOLUME 119  

 211
Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process

#6*(589.898++80792+9,58$2&6/68/90.52)6789+63819023783792390(58/9,8--87902),581168917583*7.9.89855259%451963/6047897.891743/45/9/8647623192+9
8&,856)8374-958,8471

#6*(589.898++80792+9,58$2&6/68/90.52)6789+63819023783792390(58/9,8--8794%541623917583*7.9.89855259%451963/6047897.891743/45/9/8647623192+97.588
8&,856)8374-958,8471

the rim of the pellet outer layer. Ultimately, this results in the vacancies present in the maghaemite structure (Hellwege and
exsolution of a Fe2O3-rich sesquioxide phase along the Hellwege, 1970).
chromite grain rims and cleavage planes, as shown in Figure Furthermore, chromite oxidation resulted in variations in
1b and identified in Table I. Such Widmänstatten the Cr/Fe ratio at the grain interiors and rims as a function of
intergrowths of sesquioxide phase (M2O3, with M grain location within the pellet. The unoxidized chromite had
representing a series of trivalent ions such as Cr3+, Al3+, and a Cr/Fe ratio of 1.64, which correlated well with typical Cr/Fe
Fe3+) during chromite oxidation, have been identified by ratios of South African chromite ore originating from the
various authors (Tathavakar, Antony, and Jha, 2005; Kapure Middle Group 1 and 2 seams of the Bushveld Complex
et al., 2010; Zhao and Hayes, 2010; Glastonbury et al., (Basson, Curr, and Gericke, 2007; Kleynhans, 2011).
2015). It is believed that the sesquioxide Fe2O3 phase is Chromite near the grain rim in the outer layer of sintered
initially present as metastable, intermediate maghemite pellets had a Cr/Fe ratio of 1.42 as opposed to 1.99 near the
( -Fe2O3) exsolved precipitate, which forms by changing an grain interior, which resulted from Fe diffusion from the
ABC packing into an ABAB packing by dislocations along the grain interior towards the grain rim.
(111) chromite spinel plane. The maghemite phase then
decomposes to the more stable hematite (Fe2O3) phase at   
    
elevated temperatures (> 600ºC) in the presence of oxygen Quantitative Rietveld refined XRD analysis was performed
(PO2 = 0.2 atm.) (Tathavakar et al., 2005; Pan, Yang, and on the as-received pre-oxidized chromite fines. The phases
Zhu, 2015). The presence of Al3+ cations increases the found (in order of decreasing abundance) were chromite
oxidative decomposition temperature as they can occupy 39.9 wt%, chromian spinel 42.9 wt%, haematite 5.1 wt%,


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Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process
and enstatite 12.0 wt%. The chromite phase represents containing pre-oxidized chromite fines contained a larger
residual chromite. The chromian spinel chromite formed at proportion of ultrafine particles, as is evident from a
1200ºC in the presence of oxygen. Tathavakar et al., (2015) comparison of Figures 4a and 4b. These ultrafine particles
stated that South African chromite decomposes into two filled interparticle gaps and improved particle contact, which
spinel phases upon heating, i.e. (Mg1-x,Fex)(Cr1-y,Aly)2O4 enhanced cured pellet strength. The presence of the ultrafine
and (Fe1-a,Mga)(Cr1-b,Alb)2O4. The two observed chromite particles in the pre-oxidized chromite fines can be related to
phases, i.e. chromite and chromian spinel, were in agreement the phase/chemical nature thereof. EMPA indicated that
with phases detected by Tathavakar, Antony, and Jha sesquioxide Fe2O3 phases were formed in outer layer pellet
(2015). Furthermore, the detection of hematite (Fe2O3) chromite grains (see Mechanism of chromite oxidation
indicated that free Fe2O3, which formed as described in the section, Table I) during pellet oxidative sintering.
section Mechanism of chromite oxidation, was present in the Quantitative Rietveld refined XRD analysis even indicated the
pre-oxidized chromite fines. The enstatite phase likely presence of haematite (XRD characterization of pre-oxidized
originated from siliceous gangue minerals, clay that was chromite fines section) in the pre-oxidized chromite fines.
added as a pellet binder, and ash from the coke (in-pellet Zhao and Hayes (2010), who also investigated oxidative
carbon fuel source). sintered chromite pellets, found that the phase
transformation responsible for Fe2O3 formation resulted in a
    
    shear mechanism (i.e. crystal stress/strain build-up) that can
If pre-oxidized chromite fines were to be recycled into cause crystalline mechanical break-up, thereby generating
oxidative sintered pellets beyond the current limitation of the ultrafine particles observed in the pre-oxidized chromite
4 wt% (Basson and Daavittila, 2013), such pellets must be fines (Figure 4b).
physically strong enough to prevent fines formation. Figures In addition to the particle size-related enhancement of
2 and 3 present the cured compressive and abrasion cured pellet strength, particle surface morphology was also
resistance strengths of pellets containing 4, 8, 16, 32, and considered. Surface SEM micrographs of pellets containing
64 wt% pre-oxidized chromite fines, compared to pellets zero and 16 wt% pre-oxidized chromite fines pellets are
containing zero wt% pre-oxidized chromite fines (indicated presented in Figures 5a and 5b, respectively. The most
by the y-axis). notable difference in surface morphology is the enhanced
From Figures 2 and 3, it is evident that pellet interparticle sintering of the cured sintered pellets containing
compressive and abrasion resistance strengths remained the pre-oxidized chromite fines. This suggests that some
same, or improved, compared to the base case (zero wt% pre- additional degree of melting occurred during sintering,
oxidized chromite fines) as the pre-oxidized chromite fines probably due to the presence of pre-oxidized chromite fines.
content increased from 4 to 32 wt%. However, pellets Obviously, this can at least in part be attributed to the better
containing 64 wt% pre-oxidized chromite fines were interparticle contact and reduced interparticle voids, but it
substantially weaker. It thus seems feasible to include up to was also important to investigate the chemical nature of the
32 wt% pre-oxidized chromite fines in oxidative sintered interparticle bonding. SEM-EDS analyses of the areas
pellet mixtures without adversely affecting cured pellet highlighted with the white blocks in Figures 5a and 5b
strengths. However, it is unlikely that such large additions indicated similar chemical compositions. This suggests that
would ever be required. the siliceous gangue minerals, clay as the pellet binder, and
There might be various reasons why the cured sintered ash from the coke (in-pellet carbon fuel source) jointly
pellets containing pre-oxidized chromite fines (at least up to contributed to binding the particles together via the
32 wt% containing pellets) were stronger than the base case. formation of a molten phase. Figure 6a present a SEM
However, the most obvious is that the cured sintered pellets micrograph of a typical pre-oxidized chromite fines particle,

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VOLUME 119  

 213
Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process

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while the white box in Figure 6b indicate the presence of a therefore recommend that pre-oxidized chromite fines can be
aluminosilicate type particle (SEM-EDS composition of recycled in excess of the current 4 wt% limitation, but only
4.0 wt% Al, 8.0 wt% Si, 7.7 wt% Mg, and 0.5 wt% Ca). after considering the following aspects.
Considering that the interparticle bridges in the samples with  An appropriate techno-economic study should be
and without the pre-oxidized chromite fines were conducted to assess the financial viability of the
compositionally similar, the difference in their sintered changes to the process.
compressive and abrasion strengths can most likely be  Practical implications, such as equipment
attributed to the presence of more ultrafine particles in the modifications, as well as equipment and/or process
pre-oxidized chromite fines. licensing/warranty issues. For instance, the crushing of
oversized green pellets and the operational lifetime of
230-(16231 the steel sintering belt were not considered in this
The findings presented in this paper suggest that pre- paper. Currently, oversized green pellets are crushed
oxidized chromite fines, originating from the oxidative pellet with a roller before the moist material is recycled to the
sintering scrubber, and fines screened out from oxidative pelletizing drum. This roller might be damaged by
sintered pellets may be re-introduced into the moist material larger hard particles in the pre-oxidized chromite fines
mixture that is pelletized in excess of the current 4 wt% limit if this material is mixed with the moist material that is
indicated by the technology supplier. EMPA and quantitative pelletized. This can be avoided by replacing the roller
XRD analysis verified the formation of Fe2O3-rich by a more robust crushing device, or alternatively
sesquioxide phases and/or liberated Fe2O3. Such phases will milling the pre-oxidized chromite fines with the ore and
metallize at lower temperatures during smelting compared to carbonaceous material to prevent roller damage. As
normal chromite; hence possibly enhancing metallurgical previously mentioned, increased recycling of pre-
efficiency and reducing electricity consumption. The authors oxidized chromite fines might also require higher


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Recycling pre-oxidized chromite fines in the oxidative sintered pellet production process
carbon additions in the green pellets, which could be HILL, R., and HOWARD, C. 1987. Quantitative phase analysis from neutron
shorten the operational lifetime of the steel sintering powder diffraction data using the Rietveld method. Journal of Applied
Crystallography, vol. 20, no. 6. pp. 467–474.
belt. However, our results indicate that increased
https://doi.org/10.1107/S0021889887086199
recycling of pre-oxidized chromite fines up to a very
high percentage does not adversely influence sintered ICDA. 2013. Statistical Bulletin 2013 Edition. International Chromium
pellet strength. Such decisions (how to introduce Development Association, Paris, France.

larger, hard pre-oxidized particles and the effect of KAPURE, G., TATHAVADKAR, V., RAO, C.B., RAO, S.M., and RAJU, K.S. 2010. Coal
increased recycling of pre-oxidized fines on the steel based direct reduction of preoxidized chromite ore at high temperature.
sintering belt) will be guided by the techno-economic Proceedings of the 12th International Ferroalloys Congress (INFACON
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issues. However, the possible metallurgical and energy chromite pre-reduction process – a case study. MSc dissertation, North-
benefits associated with recycling of pre-oxidized West University, Potchefstroom, South Africa.

chromite fines, which have up to now largely been KLEYNHANS, E.L.J., BEUKES, J.P., VAN ZYL, P.G., KESTENS, P.H.I., and LANGA, J.M.
ignored, should also be considered. 2012. Unique challenges of clay binders in a pelletised chromite pre-
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0
32'-8/*8)8371
KLEYNHANS, E.L.J., NEIZEL, B.W., BEUKES, J.P., and VAN ZYL, P.G. 2016. Utilisation
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