Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

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Process Safety and Environmental Protection

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Statistical analysis of the spray roasting operation for the

production of high quality Fe2 O3 from steel pickling liquors
Alex Souza Ferreira a,1 , Marcelo Borges Mansur b,
a

USIMINAS S.A., Av. Pedro Linhares Gomes, 5431, 35160-900 Ipatinga, MG, Brazil
Departamento de Engenharia Metalrgica e de Materiais, UFMG, Av. Antnio Carlos, 6627, Pampulha,
31270-901 Belo Horizonte, MG, Brazil

a b s t r a c t
Statistical tools were used to analyse the spray roasting operation so as to identify the main operating variables for
the production of commercial value iron oxide (Fe2 O3 ) by pyrohydrolysis from steel pickling liquors. The study was
carried out using a 24 factorial design of experiments and the effects of the following variables were investigated
based on large scale experimental data: temperature, liquor feed ow rate, pressure and feed air/COG (coke oven
gas) ratio. The quality of Fe2 O3 was evaluated according to the contents of Cl, Fe, Si, Mn and H2 O, as well as pH and
granulometry. For the conditions investigated, the major inuencing variables were temperature and feed ow rate;
in fact, commercial value Fe2 O3 was obtained solely at higher evaluated levels of temperature and ow rate. The
contents of Fe, Si and Mn in the Fe2 O3 were affected by the content of respective species in the feed liquor, which
in turn depends on the type of steel treated in the pickling line. Simple statistical models were proposed to describe
some Fe2 O3 characteristics. Before this study, only 10% of the Fe2 O3 produced at USIMINAS was commercialized,
due mainly to the high content of chloride (approximately 0.45%, w/w). Today, all oxide produced meets quality
requirements.
2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: HCl regeneration; Pyrohydrolysis; Iron oxide; Spray roaster; Statistical tools

1.

Introduction

The regeneration of HCl from spent hydrochloric pickle

liquors generated by the steel industry is normally performed by means of pyrohydrolysis (Harris, 1994; Steinbach
and Baerhold, 2002; Baerhold et al., 2006; Demopoulos et al.,
2008). According to this technology, bound and unbound chloride species are recovered from the acid solution by thermal
decomposition. In this process, metal chlorides hydrolyse in
the presence of air and water vapour at high temperatures to
produce HCl gas and metal oxides. The HCl is recovered by adiabatic absorption in water, thus producing a concentrated HCl
solution with a typical strength of 1618% (w/w), which is then
sent back to the pickling line. The metal oxide, on the other
hand, is a by-product that, depending on its composition, may
or may not be valuable (Harris, 1994).

Pyrohydrolysis can be applied to produce commercial

value metal oxides, such as MgO, Al2 O3 , and rare earth
compounds. However, this may not be an economically feasible option in some cases, as it can be a rather expensive
and energy-intensive technology (energy consumption ranges
between 600 and 1200 kcal/L) (Karner and Hofkirchner, 1996;
Demopoulos et al., 2008). New process options based on crystallization and hydrolytic distillation have been proposed as
alternative methods (Demopoulos et al., 2008; Al-Othman and
Demopoulos, 2009), while separation techniques, such as distillation (Tomaszewska et al., 2001), selective precipitation
(Jandov et al., 2002), membranes (Csicsovszki et al., 2005)
and solvent extraction (Ismael and Carvalho, 2003; Mansur
et al., 2008), seem to be more appropriate in treating pickling
liquors when metal composition is rather complex. However, in the particular case of pickling liquors from the steel

Corresponding author. Tel.: +55 31 3409 1811; fax: +55 31 3409 1815.
E-mail addresses: alex.ferreira@usiminas.com (A.S. Ferreira), marcelo.mansur@demet.ufmg.br (M.B. Mansur).
Received 17 March 2010; Received in revised form 29 September 2010; Accepted 27 November 2010
1
Tel.: +55 31 3829 3444; fax: +55 31 3824 6210.
0957-5820/$ see front matter 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.psep.2010.11.005

Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

173

Fig. 1 Typical ow sheet of HCl regeneration plant based on pyrohydrolysis.

industry, as predominant metal species in these solutions
are iron chlorides, pyrohydrolysis is still the technology of
choice to regenerate HCl, in turn producing Fe2 O3 as a byproduct. Pickling liquors typically contain 140220 g/L HCl
(density 12001280 g/L) and 90140 g/L of total iron, predominantly found as FeCl2 species (Mansur et al., 2008; Kladnig,
2003).
Pyrohydrolysis basically consists of the reversion of the
pickling reactions under heat. The transformation of iron chlorides into Fe2 O3 , in turn producing HCl gas, occurs at a rate of
over 99%, according to the following reactions (Kladnig, 2008):
4FeCl2(aq) + 4H2 O + O2(g) 8HCl(g) + 2Fe2 O3(s)

(1)

2FeCl3(aq) + 3H2 O 6HCl(g) + Fe2 O3(s)

(2)

High contents of FeCl3 allow for the formation of unwanted

chloride gas (Cl2 ), which can be eliminated from the stack gas
by means of a chemical reaction generated by a rinsing with
sodium thiosulphate (Na2 S2 O3 ) solution. The route consists
of four main steps (pre-concentration, roasting, absorption
and treatment of exhausted gases) as schematically shown
in Fig. 1.
In the pre-concentration step, the pickling liquor is rst
put in direct contact with the hot roast gases from the spray
roaster in a venturi evaporator where mass and heat transfers take place. Nearly 2530% of the solution is evaporated,
while 5060% of the pre-concentrated solution is re-circulated
back to the venturi to increase mass and heat transfer performances. The remaining volume is then sent to the roaster.
The roast gases are cooled down to nearly 95 C in the venturi, in turn removing any dust particles from the gas stream
not collected in the cyclone, and is then sent to the absorption
column.
In the roasting step, the pre-concentrated solution from
the venturi evaporator is injected into the spray roaster by
means of spray booms with one or more injection nozzles.
Injection occurs at the top of the reactor (pressure between
4 and 10 bars). The reactor is directly red at the bottom by
tangentially mounted burners that create an ascending hot
swirl. Temperatures inside the reactor vary between 700 C
(burner level) and 420 C (roast gas exit duct). Droplets of preconcentrated iron chloride solution are converted into solid

Fe2 O3 particles according to combined heat and mass transfer phenomena (Itoh et al., 1976; Kladnig, 2008). HCl gas leaves
the reactor through the top, while oxide is removed from the
reactor bottom by means of mechanical extraction devices. A
cyclone in the roast gas duct ensures separation and feed back
of larger oxide particles removed by the roast gas.
In the absorption column, the HCl of the saturated roast gas
exiting the venturi evaporator is adiabatically absorbed into
water or acid rinse water from the pickling line (commonly
0.5% (w/w) HCl). The regenerated HCl solution is collected
at the column bottom, while the gases leaving the top of
the column undergo treatment in the exhaust gas treatment
step. The roast gases are conveyed through the system by
means of exhaust fans that provide pressure increases of
nearly 200 mbar and are feedback-controlled to maintain a
relative pressure of 2 mbar between the reactor and the
atmosphere to avoid any overpressure-related leakage of acid
gas. To rinse the impeller and cool down the gas, as well as
to remove any remaining traces of HCl from the roast gas,
the exhaust gas fans are commonly supplied with quenching water, which is separated from the exhaust gas stream
by means of a mist eliminator on the pressure side of the
fan. In a nal scrubber, commonly consisting of a combination of wet scrubbers, such as venturi scrubbers and scrubber
columns, remaining traces of HCl and dust are removed. If
necessary, absorption chemicals, such as NaOH and Na2 S2 O3 ,
are used to bind HCl and Cl2 , which are formed under certain
circumstances in several, but not all, spray roasting reactors.
Such industrial plants are normally very compact, and
operate within a closed circuit. Consequently, slight changes
in the operation of any given equipment may interfere in the
plant performance as a whole, possibly reducing the quality of
the Fe2 O3 by-product and/or generating considerable amounts
of stack emissions containing HCl, particles and chlorine. Such
emissions have led to numerous violations of the U.S. clean
air act in the past. Therefore, the aim of the present work is
to evaluate how main operating variables contribute to the
spray roaster to produce high quality Fe2 O3 so as to attend to
commercial requirements of Cl, Fe, Si, Mn and H2 O contents
(see limits in Table 1). As complex mass and energy transfer phenomena occur simultaneously in the reactor, statistical
analysis may provide process engineers with an easier way to

174

1.30 (1.18)
0.95 (0.51)
1.00 (1.02)
0.66 (0.41)
1.25 (0.91)
0.81 (0.33)
1.40 (1.11)
1.03 (0.53)
0.87 (0.03)
1.00 (0.19)
0.86 (0.17)
0.59 (0.16)
0.34 (0.17)
0.41 (0.34)
0.43 (0.23)
0.59 (0.47)
0.43 (0.05)
0.40 (0.04)
0.42 (0.06)
0.42 (0.07)
0.46 (0.06)
0.43 (0.03)
0.46 (0.04)
0.42 (0.05)
0.42 (0.02)
0.43 (0.04)
0.41 (0.02)
0.39 (0.02)
0.49 (0.11)
0.50 (0.12)
0.50 (0.12)
0.37 (0.02)
0.03 (0.01)
0.03 (0.01)
0.03 (0.01)
0.04 (0.02)
0.04 (0.01)
0.02 (0.10)
0.03 (0.01)
0.03 (0.01)
0.05 (0.04)
0.06 (0.04)
0.04 (0.01)
0.05 (0.02)
0.07 (0.02)
0.06 (0.01)
0.05 (0.01)
0.05 (0.04)
93.1 (3.6)
90.9 (4.3)
93.4 (2.8)
91.6 (5.5)
93.9 (1.7)
95.3 (2.4)
91.0 (2.8)
95.9 (1.4)
96.8 (0.2)
96.9 (0.2)
95.6 (2.0)
95.8 (0.2)
98.5 (0.4)
97.6 (0.2)
97.7 (0.6)
97.2 (1.3)
1.05
1.25
1.05
1.25
1.05
1.25
1.05
1.25
1.05
1.25
1.05
1.25
1.05
1.25
1.05
1.25
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

430
430
430
430
430
430
430
430
470
470
470
470
470
470
470
470

85
85
85
85
100
100
100
100
85
85
85
85
100
100
100
100

25
25
15
15
25
25
15
15
25
25
15
15
25
25
15
15

0.66 (0.07)
0.71 (0.01)
0.68 (0.02)
0.64 (0.05)
0.68 (0.03)
0.64 (0.02)
0.70 (0.02)
0.67 (0.02)
0.32 (0.02)
0.30 (0.01)
0.34 (0.02)
0.37 (0.02)
0.11 (0.01)
0.16 (0.01)
0.15 (0.01)
0.18 (0.01)

Humidity (%, w/w)

MnO (%, w/w)
Chloride (%, w/w)
L ()

The level of variables was chosen according to operational

restrictions of the plant, while also taking into account the
teams experience in its operations. Once the plant had been
set to work at desired variable levels, it was left to run alone
for at least for 2 h of continuous operation in an attempt to
achieve stationary conditions. After, samples containing 100 g
of Fe2 O3 were withdrawn from the bottom of the spray roaster
for analysis. All operating variables were carefully monitored
and controlled during the experiments to avoid any substantial change that could affect the results. Tests were carried
out in triplicate, using real pickling solutions produced in the
steel pickling lines of the company (average nominal ow
rate = 4500 L/h). The total iron concentration in the liquor fed
to the spray roaster ranged from 120 to 130 g/L. The injection
nozzles of the spray roaster (consisting of 2 spray booms with
3 injection nozzles and 1 spray boom with 2 injection nozzles) were cleaned after each shift change or when any change
in the solutions from the pickling lines could be identied.
The total iron concentration in the regenerated acid leaving
the absorption column was also measured (average range of
58 g/L).
The collected Fe2 O3 samples were analysed to assess
their contents of Cl, Fe, Si, Mn and H2 O. All chemicals
used in these analyses were of analytical grade. Samples of Fe2 O3 were also dissolved in water and the pH

Table 2 Composition of Fe2 O3 produced in the spray roaster at changing conditions.

T = temperature at the top of the spray roaster: 430 C and

470 C;
Q = percent ratio between feed and maximum liquor ow
rates: 85% and 100%;
P = pressure in the spray roaster: 25 and 15 mm H2 O;
L = air/COG (coke oven gas) ratio (named lambda) = 1.05 and
1.25.

Fe2 O3 (%, w/w)

A full 24 factorial design of experiments was proposed to evaluate the effect of the following operating variables on the
quality of Fe2 O3 produced in industrial spray roasters. The
roaster considered in this study operates at the HCl regeneration plant 1 of USIMINAS (Brazil), which, together with other 2
similar plants, is able to treat up to 13,500 L of pickling liquors
per hour.

SiO2 (%, w/w)

Experimental

P (mmH2 O)

2.

Measured parameters

better understand the industrial process necessary to produce

commercial value iron oxide.
It should be emphasized that before the present study
using statistical tools, only 10% of the Fe2 O3 produced at USIMINAS was commercialized due to the high content of chloride
(approximately 0.45%, w/w). Today, all oxide produced meets
quality requirements.

Q (%)

98.50%, w/w
0.07%, w/w
0.30%, w/w
0.30%, w/w
1.00%, w/w
0.1510.00 mm
0.304.00 kg/L
0.018.00 m2 /g

T ( C)

FeO3 content
SiO2 content
Chloride content
MnO content
Humidity
Granulometry
Specic weight
Specic surface

Fixed variables

Typical range

Test

Property

pH

Table 1 Typical properties and composition of

commercial value oxide by-product.

2.7 (0.1)
2.7 (0.3)
2.8 (0.1)
2.6 (0.3)
2.9 (0.3)
3.1 (0.1)
2.9 (0.1)
2.9 (0.1)
3.4 (0.2)
3.1 (0.5)
3.2 (0.1)
3.2 (0.3)
3.4 (0.3)
3.2 (0.3)
3.3 (0.3)
3.3 (0.2)

Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

175

Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

Table 3 Signicant regression coefcients (1st and 2nd orders).

Chloride
Mean
T
Q
P
L
TQ
TP
TL
QP
QL
PL
R2

6.74
1.72 102
1.30 101

3.03 104

0.988

Fe2 O3
43.94
8.55 102
1.39 101

0.863

SiO2 *

MnO
3

5.26 10
2.16 106
2.60 104
1.18 102

2.76 105

1.06 104

0.912

5.12
1.10 102
5.37 102

1.26 104

0.858

Humidity*
32.38
6.60 102

23.44
2.11 105

5.01 102
3.25 105

0.671

pH
2.82
1.07 102
1.13 102

0.870

Coefcients were found to be correlated (p-level > 0.05).

of the aqueous phase was measured using a pH-meter.

The granulometry of Fe2 O3 was measured by laser diffraction (Malverne, model Mastersizer X). Selected samples of
Fe2 O3 were submitted to additional analysis, such as X-ray
diffraction (Rigaku equipment, model Geigerex), to identify
the predominant mineral phases within the sample; optical microscopy (Zeiss, model Axio Imager A1.M), to produce
a visual analysis of the product (25 zoom); and scanning electron microscopy (Zeiss, model EVO 50), to evaluate
details on the shape and surface of obtained iron oxide particles.

The statistical analysis of results was performed using the

STATISTICA software (version 5.1).

3.

Results and discussion

Table 2 summarizes the average contents of Cl, Fe, Si, Mn and

H2 O, as well as the pH (including standard deviations shown
in parenthesis) in the Fe2 O3 samples collected from the bottom of the spray roaster for the studied range of operational
conditions.

Fig. 2 Comparison between experimental and calculated data (calculations were using Eq. (3) and coefcients shown in
Table 3).

176

Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

Fig. 5 Content of Cl in the Fe2 O3 by-product versus pH.

Fig. 3 Dispersion of liquor in the spray roaster with ow

rate: (A) Q < 50%, (B) Q 80%, and (C) Q = 100%.
First, data shown in Table 2 were used to estimate effects of
1st and 2nd orders of studied variables; effects of 3rd and 4th
orders were found to be insignicant in previous calculations.
The following effects were found to be signicant from the
statistical point of view (R2 > 0.95 for all ttings): T and Q for
the content of Fe and pH; T, Q and TQ for the content of Cl
and Mn; T, Q, P, TP and QL for Si; and T, L, TQ, TL and QP for
H2 O. According to these results, T and Q appear to be the main
variables (for the conditions studied), as they affected the roast
operation in nearly all measured parameters; P and L were
found signicant only for Si and H2 O. However, since most of
these effects were found to be correlated (p-level > 0.05), a new
tting was performed considering only the effects which were
determined to be signicant in the rst tting. Such results
are shown in Table 3, including R2 tting coefcients.
As expected, lower R2 values were obtained in this experiment, because the number of tting coefcients was reduced;
a satisfactory tting was obtained only for Cl (R2 > 0.95). The
estimated effects for Si and H2 O proved to be correlated, thus
no statistical model was proposed for these parameters. Such
a correlation is most likely due to the relatively large standard
deviation values shown in Table 2, thus indicating no signicant change in these parameters, only uctuations around an
average value. Such behaviour may indicate some inaccuracy
in the analytical method used to quantify Si and H2 O. Based on
such results, from the statistical point of view, no signicant
effect of P and L was identied in this investigation.

Fig. 4 Content of Fe in the Fe2 O3 by-product versus

content of Fe in the pickling liquor.

The following statistical models (valid for the investigated

operating conditions) are proposed to quantify the contents of
Cl, Fe, Mn and pH (variable Y):
Y = a0 + a1 T + a2 Q + a3 TQ

(3)

The coefcients of Eq. (3) are shown in Table 3 (a0 = Mean,

a1 and a2 = 1st order, and a3 = 2nd order effect of each variable
Y). A comparison between experimental and calculated data
is shown in Fig. 2.
According to the tted coefcients shown in Table 3, the
contents of Cl, Fe and pH increase with T and Q; however,
such increase may negatively affect the content of Cl due
to a 2nd order effect (an opposite trend can be observed
in the Mn content). Therefore, to obtain a high content of
iron in the Fe2 O3 associated with the low content of Cl, the
spray roaster must operate at T = 470 C and Q = 100% (e.g.,
the respective higher values studied, Table 2). As a result, the
effect of temperature is related to the thermal decomposition
of metal chlorides which is favoured at higher temperatures. The effect of relative ow rate, on the other hand,
is related to the dispersion of the liquor drops within the
roaster. As schematically shown in Fig. 3, more efcient dispersions, and consequently smaller drops, are obtained upon
an increase in ow rate. Consequently, smaller drops are
obtained, thus favouring evaporation and the quality of the
Fe2 O3 by-product.
The content of Fe in the oxide also depends on the iron
concentration in the liquor fed to the roaster, as evidenced
by Fig. 4. The higher the iron concentration used in the solution, the higher the content of Fe in the Fe2 O3 by-product.
For the investigated conditions, the iron concentration in the
liquor must be higher than 130 g/L, thus liquors from pickling lines must be previously conditioned to achieve such a
minimum concentration before undergoing treatment in the
roaster.
The content of Si and Mn in the Fe2 O3 was found to be
related to the respective content of Si and Mn in the liquor
which, in turn, depends on the type of steel submitted to
pickling treatment. Therefore, pickling liquors must be separated in tanks and appropriately mixed before pyrohydrolysis
treatment in order to reduce their Si and Mn contents.
As regards the pH value, such a parameter is related to the
content of Cl in the oxide. In other words, the higher the pH,
the lower the Cl content (see Fig. 5). Therefore, similar to the
chloride trend, higher pH values are also expected when there
is an increase in temperature and ow rate.
Depending on the size of the particles, Fe2 O3 by-products
can be used as sinter or pellets. Within the investigated con-

Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

177

Fig. 6 Granulometry of Fe2 O3 by-product at changing temperature and ow rates (optical microscope, 25): (A) T = 430 C,
Q = 85%; (B) T = 430 C, Q = 100%; (C) T = 470 C, Q = 85%; (D) T = 470 C, Q = 100%.

ditions, analysed samples showed small particles of varying

sizes with an average of (167 55) m. A qualitative effect
in temperature and ow rate on the granulometry of iron
oxide can be seen in Fig. 6; smaller particles were obtained
at higher temperatures and ow rates. Fig. 7 shows an iron
oxide particle and, as evidenced by the thermal decomposition mechanism proposed by Itoh et al. (1976), the increase
of pressure inside drops due to evaporation results in hollow spherical particles of hematite (Fe2 O3 ) ranging from 100
to 200 m, thus corroborating with previous investigations
(Kladnig, 2008). Such particles of Fe2 O3 contain a low mechanical resistance, which might partially explain the varying sizes
obtained. Therefore, to reduce breakage, particles must be
transferred under negative pressure within the oxide bin, and
must likewise be vacuum-packed to avoid dust accumulation
within the plant.

Fig. 7 SEM micrograph of Fe2 O3 by-product (200 zoom).

4.

Conclusions

In this paper, the quality of Fe2 O3 produced by pyrohydrolysis in an industrial spray roaster was investigated using a 24
factorial design of experiments. Simple statistical tools were
used to solve an industrial problem, thus resulting in better
process efciency and a reduction in the generation of wastes.
The following conclusions can be drawn:

The main operating variables affecting spray roast operations are temperature and ow rate, thus corroborating
with previous studies (Harris, 1994; Kladnig, 2003; Steel
and Patrick, 2004). The effect of pressure and lambda
were found to be statistically insignicant for the investigated conditions. Commercial value Fe2 O3 can be
obtained with an increase in both temperature and ow
rate. Likewise, an increase in temperature favours the
thermal decomposition of metal chlorides, whereas an
increase in ow rate favours the dispersion of drops.
Both variables also affect the granulometry of the Fe2 O3
by-product.
The content of Fe, Si and Mn in the iron oxide by-product
depends, respectively, on the content of Fe, Si and Mn in
the spent pickling liquor fed to the spray roaster. Hence,
the operations in the pickling lines and the storing sector
of pickling liquors must be considered in order to produce
Fe2 O3 with a high content of Fe and low contents of Si and
Mn.
Statistical models valid for the investigated operational
conditions were proposed to anticipate some iron oxide
characteristics.
Hematite was the only mineral species found in the Fe2 O3
particles produced in the studied industrial process.

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Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 172178

Acknowledgements
The authors wish to thank USIMINAS S.A. for providing the
funding for this work and the team involved in the plant
tests and laboratory analyses, M.D. Cypreste, G.A. Oliveira, J.G.
Souza, E.R.A.R. Souza, M.A.B. Borges, M. Silva, K.A.F. Castro,
G.C. Guimares, G.P. Miranda and W.S.A. Assunco, as well as
M. Maciel and J. Weslei from Sankyu.

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