J. Cent. South Univ.

(2014) 21: 32413246

DOI: 10.1007/s11771-014-2296-6

Characterization and recycling of nickel- and chromium-contained
pickling sludge generated in production of stainless steel

LI Xiao-ming()
1
, XIE Geng()
1
, HOJAMBERDIEV Mirabbos
2
,
CUI Ya-ru()
1
, ZHAO Jun-xue()
1


1. School of Metallurgical Engineering, Xian University of Architecture and Technology, Xian 710055, China;
2. School of Materials Science and Engineering, Xian University of Architecture and Technology,
Xian 710055, China

Central South University Press and Springer-Verlag Berlin Heidelberg 2014


Abstract: Pickling sludge generated during the neutralization of pickling wastewater with calcium hydroxide in stainless steel
pickling process was characterized using X-ray fluorescence spectrometry, X-ray diffractometry, scanning electron microscopy,
thermogravimetry and differential scanning calorimetry, etc. The major compositions of pickling sludge are CaF
2
, CaSO
4
, Me(OH)
n
(M: Fe, Cr, Ni), and the content of CaF
2
is high in the sludge. The melting point of pickling sludge is about 1350 C and the viscosity
is about 0.14 Pas at 1450 C, which are comparatively lower than those of normal refining slag. After heat treatment, the contents of
sulfur and fluorine in the pickling sludge were reduced, confirming the thermal decomposition of sulfate in the sludge. Fluorine in the
sludge is reduced by the gaseous SiF
4
and AlF
3
generated through the reactions of CaF
2
with SiO
2
and Al
2
O
3
. The preliminary results
from the reduction test indicate that the sulfur content in the steel is not affected by the presence of sulfur in the sludge. The recovery
of nickel is about 40%, and the chromium content changes marginally due to the protective atmosphere under the reduction condition
of chromic oxide. The pickling sludge is a potential auxiliary material for the production of stainless steel.

Key words: stainless steel; pickling sludge; characterization; recycling; sulfur; fluorine



1 Introduction

Pickling process is normally applied in the stainless
steel production to improve the corrosion resistance of
stainless steel. Electrolytic pickling in Na
2
SO
4
electrolyte
is extensively used in the modern pickling process due to
excellent surface finish, low operating and maintenance
costs, etc [1]. The pH of the electrolyte used is normally
modified to faintly acid. In addition, the mixture of nitric
acid and hydrofluoric acid is the most efficient
electrolyte for the pickling of stainless steel [23]. The
pickling wastewater formed during the rinsing of steel
product is traditionally treated by chemical reduction and
precipitation process [45], in which the reducing agent
is added into the wastewater under acidic conditions in
order to reduce Cr
6+
to Cr
3+
, followed by the addition of
lime or sodium hydroxide in order to generate a
chromium hydroxide precipitation. Finally, the
precipitate is pressed into a filter cake

[6], namely the
pickling sludge.
After precipitation process, pickling sludge still
contains significant amount of Cr
6+
and fluoride, which
have a potential danger to human health and the
environment [78]. Solidification/stabilization treatment
is the most commonly applied way to deal with pickling
sludge at present. However, the Cr
6+
cannot be removed
completely by this process [911], and other valuable
metals cannot be recycled.
The recovery of heavy metals from pickling sludge
through hydrometallurgical process has been studied in
recent years. CHEN [12]

demonstrated a method for the
effective separation of nickel and chromium in the sludge
from different ions, such as calcium, iron and others
through a salt method. The recycling of pickling sludge
was realized through several reaction pools with different
pH values and ion-exchange method. LIU et al [13]
reported that the manganese, chromium, nickel and other
toxic metals in the pickling wastewater can be leached by
sulfuric acid. In the pyrometallurgical process, different
residues, such as sludge and dust could be disposed by
IMETCO process [14] but pickling sludge with high
CaF
2
was excluded in this method [7]. MA et al [7]
reported that the reduced metals predominantly existed

Foundation item: Project(2010JM7010) supported by the Natural Science Foundation of Shaanxi Province, China; Project supported by the Scientific
Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, China; Project supported by the Technology
Foundation for Selected Overseas Chinese Scholars, Department of Human Resources and Social Security of Shaanxi Province, China
Received date: 20130422; Accepted date: 20130701
Corresponding author: LI Xiao-ming, Professor, PhD; Tel: +862982202923; E-mail: xmli88@126.com
J. Cent. South Univ. (2014) 21: 32413246

3242

in the form of alloys, such as Fe-Ni and Cr-Fe-Ni, when
petrol-coke was used as reductant. Similar result was
found in the reduction of pickling sludge with the
addition of EAF dust and iron scale [15]. XU [16]
succeeded in separating chromium and iron from the
pickling sludge by heat treatment at high temperature.
However, recycling of the pickling sludge within
stainless steel refining furnace is the most promising way
to treat these wastes. The pickling sludge contains a very
high amount of calcium fluoride (CaF
2
), which is
commonly used as a metallurgical auxiliary material.
Once the pickling sludge is added to the stainless steel
refining furnace, it will positively not only reduce the
consumption of fluorspar, but also achieve the
comprehensive utilization of Ni, Cr and Fe in the sludge.
To investigate the feasibility of pickling sludge as
an auxiliary material for the production of stainless steel,
the moisture content, chemical composition, phase,
microstructure, thermal behavior, melting point and
viscosity were determined. Then, the quantitative
pickling sludge reduction test was performed.

2 Experimental

The sample of pickling sludge obtained from a
stainless steel plant in China is shown in Fig. 1. It is
usually generated from the pickling process of stainless
steel with the HF and HNO
3
.


Fig. 1 Photograph of pickling sludge sample

The as-received pickling sludge contained a certain
amount of water, which was not conducive to perform
the experiments. Hence, 1 g and 3 g of fresh pickling
sludge were dried at 105 C and 200 C, respectively, in
a drying oven to measure its moisture content. The mass
loss was recorded every 10 min until the mass became
constant. In addition, the total mass loss of 100 g of dried
pickling sludge was determined after heat treatment at
700 C and 1200 C.
Pickling sludge was dried at 105 C for 2 h and
ground into powder with size of about 150 m. The
chemical composition of powder sample was analyzed
using RIX2000 X-ray fluorescence spectrometer (Rigaku,
Japan). The crystalline phases of dried pickling sludge
were identified using X-ray diffraction. Copper K

radiation (40 kV and 40 mA) was used as the X-ray
source. The morphology of the dried and heat treated
pickling sludge samples were determined using
JSM-6390 scanning electron microscope (JEOL, Japan),
equipped with an energy dispersive X-ray spectrometer
(EDS), at an acceleration voltage of 15 kV.
The thermal behavior of the dried pickling sludge
sample was studied by thermogravimetry (TG) and
differential scanning calorimetry (DSC), using STA 449
Jupiter (Netzsch, Germany). Sample was heated from
30 C to 1400 C with heating rate of 10 C/min in
nitrogen atmosphere.
The dried pickling sludge was ground with the
addition of a proper amount of dextrin and water as
binder and moisturizer. The ground sample was
uniaxially pressed into cylindrical samples with 3 mm in
diameter and 3 mm in length. The melting point of dried
cylindrical samples was measured using M-565 melting
point analyzer (BCHI Labortechnik AG, Switzerland).
The viscosity of dried pickling sludge was measured by
RSV-1600 viscometer (Orton, USA) at various
temperatures.
Quantitative pickling sludge reduction test was
performed with the mass ratios of pickling sludge to
calcium fluoride of 1:1 and 3:1 (98.5% in purity and 0
3 mm in particle size), respectively. A certain amount of
lime (98% in purity and 03 in mm particle size) was
also introduced to maintain the basicity of slag, and extra
silicon (99% in purity and 03 mm in particle size) was
added for the reduction of metals from the pickling
sludge. Stainless steel, calcium fluoride, pickling sludge
(melted at 1200 C), silicon and calcium oxide were
weighed and mixed. The mixture was then put into the
corundum crucible, which was contained in the graphite
crucible, and heated up to 1600 C. After the experiment,
the chemical composition of molten steel was analyzed.

3 Results and discussion

3.1 Moisture content of pickling sludge
The change in moisture content of pickling sludge
was determined based on the mass loss of the sample
during a drying process. The results are shown in Fig. 2.
The moisture content of pickling sludge is approximately
60.4%, and the drying time of pickling sludge is reduced
by increasing drying temperature or decreasing of sample
amount.

3.2 Chemical and phase composition of pickling
sludge
The chemical composition of pickling sludge is
given in Table 1. The contents of fluorine, iron, calcium
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Fig. 2 Changes of moisture content of pickling sludge during
drying process: (a) In different masses; (b) At different
temperatures

Table 1 Chemical compositions of pickling sludge (mass
fraction, %)
Cr Ni Fe Ca Si F
3.37 1.5 13.6 22.8 2.063 22.2
S Na Mg Al C O
1.96 0.269 0.352 0.25 0.936 30.7

and sulphur are high in the pickling sludge, while the
contents of nickel and chromium are relatively low. The
X-ray diffraction (XRD) pattern shown in Fig. 3(a)
indicates that the CaF
2
, CaSO
4
, CrF
2
and CaCO
3
are
predominant phases in pickling sludge. Amorphous metal
oxide phase and stainless steel scale also present in
pickling sludge. No nickel-containing phase is observed
on the XRD pattern due to the low concentration.

3.3 Microstructure of pickling sludge
The morphology of pickling sludge is shown in
Fig. 3(b). The ground pickling sludge consists of tiny
particles of CaF
2
, CaSO
4
, CrF
2
, CaCO
3
and the oxides of
iron, chromium and nickel [17]. The CaF
2
and CaSO
4

phases presumably form in the neutralization and
reduction processes. It is believed that the metal oxide


Fig. 3 XRD pattern (a) and SEM micrograph (b) of pickling
sludge after drying at 105 C

rich precipitate is the reaction product between the metal
ions and lime during the final precipitation process.

3.4 TG-DSC analysis
Figure 4 shows the TG-DSC curves of high
temperature behavior of pickling sludge. Approximately
20% of mass loss is observed in the temperature range of
301400 C. The mass loss below 300 C is due to the
loss of moisture at 100 C and dehydration up to 300 C.


Fig. 4 TG-DSC curves of pickling sludge after drying at 105 C
J. Cent. South Univ. (2014) 21: 32413246

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The mass loss becomes more evident in the temperature
ranges of 620700 C and 9001100 C. The mass loss
of 0.8% observed in the temperature range of 620
700 C is attributed to the release of SO
2
and SO
3
from
the decomposition reaction of sulfates. The mass loss of
about 2.86% in the temperature range of 9001100 C is
due to the formation of SiF
4
and AlF
3
in the reactions of
CaF
2
in pickling sludge with SiO
2
and Al
2
O
3
.

3.5 Melting point and viscosity of pickling sludge
Figure 5 shows the changes in the form of pickling
sludge at different temperatures ranging from 503 to
1350 C. The melting temperature of pickling sludge is
about 1350 C. Calcium fluoride is used as a co-solvent.
The melting point of pickling sludge is reduced with
increasing the content of calcium fluoride. In the
previous reports, the melting point of slag containing
CaO and CaF
2
is 14001500 C when the content of
CaF
2
is 20%30%. Therefore, the melting point of
pickling sludge is comparatively lower, making it more
conducive to melting and to the mobility improvement of
slag. The viscosity of pickling sludge is shown in Fig. 6.
The viscosity of pickling sludge is 0.145 Pas at 1450 C,
and the viscosity of pickling sludge decreases with the
decrease in temperature. It can also be seen that the
whole trend decreases with increasing temperature,
which is slightly different from the theoretical point of
view, because of the compositional change during the
heating process. If the viscosity of molten slag is high, it
would have a poor fluidity and is unfavorable for the
separation of the melt from slag. On the other hand, the
low viscosity of molten slag will corrode the refractories
of furnace lining and reduce the furnace life. The slag
with 15%40% calcium fluoride has low viscosity
(0.30.5 Pas) at 13001500 C. By comparison, the
viscosity of pickling sludge in this experiment is lower
for the higher content of calcium fluoride.

3.6 Effect of heat treatment
Pickling sludge is heat treated at 700 C and
1200 C as the result of significant mass losses of
pickling sludge taking place in the temperature ranges of
620700 C and 9001100 C. The mass loss rate of
pickling sludge is 60.7% at 700 C, and the loosely
sintered aggregate with low mechanical strength is
obtained from pickling sludge. The mass loss rate of
pickling sludge is 62% at 1200 C, and the sintered
aggregate has a higher mechanical strength. With further
increasing the temperature, the mass loss rate of pickling
sludge and volatilization increase. The morphologies of
pickling sludge heat treated at 700 C and 1200 C are
shown in Fig. 7. The sintered aggregate from pickling
sludge at 700 C has similar microstructure with raw
pickling sludge, i.e. the microstructure is not affected by
heat treatment at low temperature. In contrast, the
sintered aggregate from pickling sludge at 1200 C
possesses an unlike microstructure showing the
precipitation of some crystalline phases. The contents of
sulfur and fluorine in pickling sludge heat treated at
different temperatures are given in Table 2.
Compared with the fluorine content in pickling
sludge dried at 105 C, the fluorine content in pickling
sludge heat treated at 700 C and 1200 C is significantly
reduced as the result of the generation of gaseous SiF
4

and AlF
3
by the reactions of CaF
2
with SiO
2
and Al
2
O
3
,
respectively. The sulfur content in pickling sludge also
decreases with the increase of heat treatment temperature,
which is due to the generation of SO
2
gas during the


Fig. 5 Changes in sample form of pickling sludge at different temperatures
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Fig. 6 Viscosity of pickling sludge as a function of temperature


Fig. 7 Microstructures of pickling sludge heat treated at 700 C
(a) and 1200 C (b)

Table 2 Sulphur and fluorine contents in sludge at different
temperatures (mass fraction, %)
Element 105 C 700 C 1200 C
S 1.45 0.508 0.46
F 17.47 14.77 7.96

decomposition of FeSO
4
and CaSO
4
present in pickling
sludge at 700 C and 1200 C, respectively. The removal
of sulfur in pickling sludge during heat treatment is
almost up to 70%. The sulfur content in pickling sludge
heat treated at 1200 C is about 0.46%, which does not
fully meet the requirement. Nevertheless, the following
reduction test proves that the addition of this sintered
aggregate containing 0.46% sulfur in the refining process
does not influence the final sulfur content of the steel.

3.7 Reduction test
The chemical compositions of steel samples
prepared with 50% and 75% of pickling sludge are
comparatively shown in Fig. 8. The manganese content
is significantly higher in the reference sample than that in
the steel samples prepared with pickling sludge. The
contents of sulfur, phosphorus, iron, chromium and
nickel in all of the three samples are almost the same.
Particularly, the final sulfur content of the as-prepared
steel samples is not affected by the sulfur content in
pickling sludge. When adding the pickling sludge as the
auxiliary material, the silicon content increasing in
molten steel is mainly due to the dissolution of reducing
agent silicon, while the manganese content decreasing is
caused by the oxidation of manganese existing in liquid
stainless steel. The phosphorus content is constant as the
result of low basicity under laboratory conditions,
thereby hindering the dephosphorization. The reason for
the unchanged concentration of sulfur might be that the
sulfate in sludge is relatively stable under laboratory
conditions, or that the carbon content is low in molten
steel. Due to the protective atmosphere below the
requirement of the refining furnace condition, oxidation


Fig. 8 Chemical composition of steel prepared with addition of
pickling sludge: (a) Cr, Ni, Fe; (b) C, Si, Mn, S, P
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3246

of reductant silicon and relatively low reduction
temperature under laboratory conditions, the reduction
amount of NiO, Cr
2
O
3
, Fe
2
O
3
existing in the sludge is
decreased, which may lead to the content of Ni, Cr and
Fe not varying significantly.

4 Conclusions

1) Pickling sludge has high moisture content (about
60.4%). The major compositions of pickling sludge are
CaF
2
, CaSO
4
and other metal oxides.
2) TG/DSC analysis shows that the total mass loss
of pickling sludge is about 20% as the result of the
removal of H
2
O, SO
2
, SO
3
, fluorine, calcium and silicon
during reactions.
3) The melting point of pickling sludge is 1350 C
and the viscosity is 0.14 Pas at 1450 C, which are lower
than those of normal refining slag. The pickling sludge is
more favorable for melting and improved mobility of
slag.
4) The subsequent heat treatment causes the
reduction of sulfur and fluorine in the pickling sludge
samples. Fluorine content and sulfur content decrease to
54.4% and 68.3%, respectively, when pickling sludge is
heated from 105 C to 1200 C.
5) The recovery of nickel is about 40%, and the
chromium content remains almost unchanged in the
quantitative pickling sludge reduction test due to the
protective atmosphere under the reduction condition. The
addition of sintered sludge containing 0.46% sulfur does
not influence the final sulfur content of the steel. The
pickling sludge is a potential auxiliary material for the
production of stainless steel.

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