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Emission reduction research and development of PCDD/Fs in the iron ore

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 Process Safety and Environmental Protection 117 (2018) 82–91

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Emission reduction research and development of PCDD/Fs in the iron

ore sintering
Lixin Qian a , Tiejun Chun a,∗ , Hongming Long a,b,∗∗ , Jiaxin Li a , Zhanxia Di a , Qingmin Meng a ,
Ping Wang a
a
School of Metallurgical Engineering, Anhui University of Technology, Ma’anshan, Anhui, 243032, China
b
Key Laboratory of Metallurgical Emission Reduction & Resources Recycling, Ministry of Education, Anhui University of Technology, Ma’anshan, Anhui,
243002, China

a r t i c l e i n f o a b s t r a c t

Article history: Iron ore sintering process is an important sector for iron and steel industry as well as a major pollution
Received 30 December 2017 emission source of PCDD/Fs. The PCDD/Fs emission of sintering process has not been properly controlled
Received in revised form 3 April 2018 because the flue gas presents the following characteristics, including large amount, remarkable flow
Accepted 22 April 2018
fluctuations and lower concentration. The generation mechanism of PCDD/Fs in the iron ore sintering
Available online 25 April 2018
was discussed systematically and the new developments and technologies of PCDD/Fs emission reduction
were also summarized from the source, process and the end treatments. Commonly, the PCDD/Fs formed
Keywords:
in drying and preheating zone is transferred to the lower part of the material layer which is a chemical
Iron ore sintering
PCDD/Fs
transfer process in the iron ore sintering. Finally, the potential future development of PCDD/Fs emission
Generation mechanism reduction in the iron ore sintering was also pointed out.
Emission reduction © 2018 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2. The iron ore sintering process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3. Formation mechanism of PCDD/Fs in sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.1. Formation of dioxin in a sintering bed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.2. The distribution of dioxin in the sintering machine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4. Measures to reduce dioxin in iron ore sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.1. Source control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.2. Process control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.1. Optimum operating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.2. Sintering exhaust gas recirculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.3. Additive inhibitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.3. End treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

∗ Corresponding author.
∗∗ Corresponding author at: School of Metallurgical Engineering, Anhui University of Technology, Ma’anshan, Anhui, 243032, China.
E-mail addresses: springcsu@126.com (T. Chun), yaflhm@126.com (H. Long).

https://doi.org/10.1016/j.psep.2018.04.014
0957-5820/© 2018 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
Table 1
Major toxic homologues and TEFs of dioxin.
PCDF TEF PCDD
2,3,7,8-TCDF 0.1 2,3,7,8-TCDD
1,2,3,7,8-PeCDF 0.03 1,2,3,7,8-PeCDD
2,3,4,7,8-PeCDF 0.3 1,2,3,4,7,8-HxCDD
1,2,3,4,7,8-HxCDF 0.1 1,2,3,6,7,8-HxCDD
1,2,3,6,7,8-HxCDF 0.1 1,2,3,7,8,9-HxCDD
2,3,4,6,7,8-HxCDF 0.1 1,2,3,4,6,7,8-HpCDD
1,2,3,7,8,9-HxCDF 0.1 OCDD
1,2,3,4,6,7,8-HpCDF 0.01 OCDF
1,2,3,4,7,8,9-HpCDF 0.01 – –
1. Introduction
Iron and steel industry has been an important fundamental
industry in economy of China in the last decades. The sintering
plant is an important part of the steelmaking process chain. It pro-
vides a large amount of low cost, stable quality sinter for the blast
furnace, but also causes the huge environmental pollution (Chen
et al., 2015; Guerriero et al., 2009; Long et al., 2015). The pollu-
tants discharged from a sintering plant are mainly particulates, SO2 ,
COx, NOx, HCl, fluoride and dioxin (Chen et al., 2009; Chun et al.,
2017; Jian et al., 2011; Long et al., 2012; Rizwanul Fattah et al.,
2014) as well as dioxin-like compounds including polychlorinated
biphenyles, chlorobenzenes and polychlorinated naphthalenes (Liu
et al., 2012; Liu et al., 2013a,b,c). Generally, the dioxin is abbre-
viations of polychlorinated dibenzo-p-dioxins (PCDDs, it is a ring
ether) and polychlorinated dibenzofurans (PCDFs, it is an aromati-
cally substituted furan) (Gullett et al., 2000; Kawasaki et al., 2006;
Zhao et al., 2015), which are collectively known as PCDD/Fs. It
is a tricyclic aromatic compound, comprising one or two oxygen
atoms joining with two chlorosub-stituted benzene rings and Fig. 1
shows their chemical structural diagrams (Quaß et al., 2004). In
addition, the dioxin as a class of persistent environmental organic
hormones, with teratogenicity, carcinogenicity and mutagenicity
(Chagger et al., 2000; Menad et al., 2006; Wei et al., 2017). Due
to the differences in toxic equivalency factors (TEFs) for dioxin-like
compounds, the World Health Organization reevaluation of human
and Mammalian TEFs for dioxins and dioxin-like compounds based
on the toxicity equivalent of the most toxic 2,3,7,8–TCDD in 2005
(Van den Berg et al., 2006). The details are shown in Table 1.
According to the dioxin emission report (Lv et al., 2008), the sin-
tering process is the main emission source of dioxin in the iron and
steel industry. The estimated distribution and emissions of dioxin
in different areas of China are shown in Fig. 2. Iron ore sintering
process is the second to the municipal waste incinerator toxic pol-
lutants emission source and more than 50% of dioxin emissions are
from sintering process in the iron and steel industry (Cang et al.,
2014; Cieplik et al., 2003). However, due to the sintering flue gas has
the characteristics of complex composition, large flow and low pol-
lutant concentration, the dioxin of sintering process has not been
fully controlled. So the dioxin emissions in the industry increasing
year by year, and dioxin emission reduction of the sintering process
is pushed on the cusp.
The aim of this article is to provide a brief overview of the gen-
eration mechanism of dioxin with the characteristics of an iron ore
sintering process and the development of source, process and the
end treatments emission reduction was discussed.
2. The iron ore sintering process
Fig. 3 shows a schematic diagram of the major processes in a typ-
ical iron ore sintering plant. It consists of an agglomeration through
an oxidizing/reducing fusion of iron ore fines, fluxes (lime, lime-
stone etc.), and typically 3–5 wt% solid fuels (coke fines and coal
83
fines) as well as re-circulated material (dust, sludge, etc.), formed
into pellets with typically 6–7 wt% moisture content and placed
TEF on a moving bed to a depth of 0.4–0.7 m at temperatures between
1 1200 and 1400 ◦ C (Thompson et al., 2016). As the bed travels under
1 an ignition hood, coke/coal particles on the upper surface are set
0.1 alight to generate a narrow flame front. Air is continuously drawn
0.1 through the bed by large fans and this causes the flame front to
0.1
descend down the bed. The flue gas is introduced into electrostatic
0.01
0.0003 precipitator and flue gas desulfurizer and then is discharged into
0.0003 stack (Abreu et al., 2015; Ooi et al., 2008a,b).
Because of the airflow continues through the material layer in
the sintering process, a continuous temperature range from high
temperature to low temperature is formed in the material layer and
presents a two-dimensional steady-state reaction process (Kasai
et al., 2000). According to the temperature change and the differ-
ence of chemical reaction in the sintering process, the material layer
is divided into different regions along the height of the material
layer, as shown in Fig. 4. The material layer takes the combus-
tion zone which the upper half distributed with sinter zone and
the lower half covered with preheating and drying zone and wet
zone as a core. The combustion zone is the highest temperature
zone with temperature up to 1300 ◦ C in the sintered material layer,
which can cause a chemical reaction and liquid phase consolidation
of the sintering mixture. The heat air generated by the combustion
zone passes downwards from the combustion zone by an induced
draught fan. Then the moisture in the mixture is heated and evapo-
rated to form a drying and preheating zone that the temperature is
100–700 ◦ C. Finally, the airflow formed a wet zone by condensing
in the lower part of the drying and preheating zone. The sinter-
ing process is completed when the combustion front reaches the
bottom of the bed (Ooi and Lu, 2011).
3. Formation mechanism of PCDD/Fs in sintering
Dioxin is decomposed above 800 ◦ C, and the decomposition rate
of dioxin is positively correlated with the temperature (Fujimori
et al., 2016; Tan and Neuschütz, 2004). Clement et al. (1988) found
that the distribution characteristics of dioxin homologues are com-
pletely different in the input and output of combustion process.
Kasai et al. (2008) found that dioxin in the soil can be decomposed
at high temperature during combustion and Abad et al. (2002) con-
firmed this view in the incinerator. He reported that the dioxin from
combustion process is largely re-synthesis in the combustion pro-
cess. At present, understanding of dioxin formation in sintering is
mostly adapted from waste incineration, as dioxin is originally dis-
covered in emissions from this process. From studies performed,
two pathways have been proposed: (i) precursor pathway and (ii)
de novo synthesis (Clement et al., 1988).
3.1. Formation of dioxin in a sintering bed
Precursor pathway explains the generation of dioxin by
chlorine-containing precursor compounds, such as chlorobenzenes
and polychlorinated biphenyls, by the Ullmann reaction in an alka-
line environment or by a direct catalytic reaction, either in the gas
phase or on the surface of particles (Gullett et al., 1992). De novo
synthesis involves dioxin formation from macromolecular resid-
ual carbon and polycyclic aromatic structures on a fly ash surface
under a low-temperature (about 300–350 ◦ C) partial oxidation in
the presence of Cl2 and metal catalysts (Sun et al., 2016).
Sintering process meets most of the conditions of de novo syn-
thesis. Because the temperature is in the range of 250–500 ◦ C with
an oxidizing atmosphere during the iron ore sintering. In addition,
the sintering raw materials and fuels contain a large quantity of
solid waste containing iron, carbon, chlorine and copper, such as
84 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
Fig. 1. Structural formulas of PCDDs and PCDFs.
Fig. 2. Emissions of dioxin in different areas in China (Liu et al., 2013a,b,c).
the blast furnace and other steelmaking dusts and so on. They pro-
vide carbon, chlorine source and catalyst conditions for de novo
reaction of dioxin. Therefore, it is generally believed that the de
novo synthesis is the main generation mechanism of dioxin in sin-
tering process (Addink and Olie, 1995; Hu et al., 2012; Kasai et al.,
2001; Kasama et al., 2006a,b; Kilgroe, 1996; Li et al., 2017; Long
et al., 2010; Nakano et al., 2009; Tan et al., 2012).
Fig. 4 shows that there is a temperature range of 250–500 ◦ C in
both the cooling area of the sinter zone and drying and preheating
zone where the dioxin can be formed in sintering process (Abad
et al., 2002; Łechtańska and Wielgosiński, 2014; Nakano et al.,
2009). The dioxin formed in the cooling area of the sinter zone is
transported downwards to the combustion zone with the suction
airflow. The temperature of the combustion zone is 1100–1300 ◦ C,
where the dioxin is decomposed in a few microseconds. Nakano
et al. (2009) observed high levels of dioxin in the drying zone of
an interrupted sintering bed, 10–30 mm in front of the flame zone.
This suggests that dioxin is formed in the drying zone ahead of the
flame front, where the temperature is between 200 and 650 ◦ C. And
the point of dioxin formation is more likely to be closer to the flame
front where the temperature, oxidation partial pressure, a lot of car-
bon, chloride and salts of transition metals are conducive for dioxin
formation (Hu et al., 2012; Nakano et al., 2009; Suzuki et al., 2004).
Therefore, it is generally considered that the drying and preheating
zone is the main forming area of dioxin. In addition, at the end of
the sintering machine, as the flame front reaches the bottom of the
sinter bed, the temperature in the several bellows at the end of the
sintering machine can reach 300–400 ◦ C. So the de novo synthesis
is occurred on the surface of the fly ashes and forms the dioxin in
the exhaust gas (Łechtańska and Wielgosiński, 2014).
3.2. The distribution of dioxin in the sintering machine
Kasama et al. (2006a,b) studied the dioxin emissions of exhaust
gas at the Oita No. 1 sintering plant. It has twenty-one wind box
and the concentration of dioxin in the flue gas of final wind boxes
is shown in Fig. 5. Both dioxin and furan show a high peak in wind
box No. 19. Furan is released broadly in the wind boxes from No.13
to No.21, and a moderate peak of its release is seen in No. 17 wind
box. It seems that the drying zone begins to reach the grate sur-
face near the sinter cake discharge side of wind box No.15 when
the exhaust gas temperature reaches 100 ◦ C. Therefore, it is sug-
gested that this part of the dioxin is formed on the surface of dust
with organic substances and chlorine supplied from incompletely
sintered areas in wind box. Tan and Neuschütz (2004) used the 14
chemical reaction equations which are about the dioxin formation
to establish a computational fluid dynamics (CFD) model of iron
ore sintering. It was also verified that dioxin could be formed in the
wind boxes by the model.
According to the distribution emission characteristics of dioxin
in sintering machine, it is believed that the process of dioxin formed
in the drying and preheating zone and transferred to the lower part
of the material layer as the flame front moved down might be a
chemical transfer process. During the process, the dioxin accumu-
lated in wet zone is decomposed and its cleavage product or catalyst
is transferred to the lower part of the layer with the suction air-
flow. When the temperature of flue gas is cooled to 250–500 ◦ C,
the dioxin is resynthesized and accumulated in wet zone, which
would be confirmed later.
4. Measures to reduce dioxin in iron ore sintering
The approaches of emission reduction of dioxin in iron ore sin-
tering process mainly include three aspects: source control, process
control and end treatment.
4.1. Source control
Source control is by reducing the sensitive elements or sub-
stances in sintering raw materials to achieve the purpose of
dioxin emission reduction. Copper, chlorine and other elements
are the key factors in the formation of dioxin in the sinter-
ing process. Among them, the transition elements Cu and other
metals are the catalyst for the formation of dioxin and pro-
mote the occurrence of Deacon and Ullmann reactions (Liu et al.,
2013a,b,c; Ryan and Altwicker, 2004; Zhang et al., 2015). Ryu (2008)
reported that the chlorine provided by CuCl2 for the formation
of dioxins would accelerate the Deacon reaction. Takaoka et al.
(2005) claimed that the formation of polychlorinated biphenyls
and chlorobenzenes was closely correlated with the presence of
 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91 85

Fig. 3. Schematic diagram of the major processes (Aries et al., 2006).

Fig. 4. The iron ore sintering process and dioxin formation mechanism.

CuCl2 ·3Cu(OH)2 . And he (Takaoka, 2010) used the sinter pot test
device to study the effect of CuO and CuCl2 on the formation of
dioxin in sintered flue gas, all of them showed a significant pro-
moting effect, and the catalytic effect of CuCl2 is stronger. Sun
et al. (2016) reported copper additives can promote formation
of chlorobenzenes and polychlorinated biphenyls in the thermal
treatment of simulated fly ash. The catalytic activity of copper com-
pounds followed the orders: CuCl2 ·2H2 O » Cu2 O > Cu > CuSO4 > CuO
for chlorobenzenes and CuCl2 ·2H2 O » Cu2 O > CuO > Cu > CuSO4 for
polychlorinated biphenyls. Among all Cu catalysts, CuCl2 is the
mostactive, because in addition to acting as a catalyst, it also serves
as a chlorine source(Yan et al., 2012). Therefore, the sintering pro-
duction should choose the iron ore of lower copper as raw materials.
Chlorine is an essential element for the formation of dioxins
(Gullett et al., 2000). The Cl content in secondary resources dust and
scale is relatively high, if them are mixed into sinter mixtures will
promote the dioxin formation (Łechtańska and Wielgosiński, 2014).
Nakano et al. (2009) used 5% EP dust, 5% BF dust and 5% purchased
scale which contain high-chlorine to sinter, then the generating
amplification coefficients of dioxin was 28, 4, and 4 respectively. It
also confirms that metallurgical dust is an important inducement
of dioxin formation. When the content of Cl element increased
from 0.04% to 0.06%, the concentration of dioxin was enhanced
(TEQ) from 0.55 to 0.82 ng/m3 (Ryan and Altwicker, 2004). There-
fore, avoiding the addition of dust or dechlorination pretreating can
achieve source emission reduction of dioxin in the sintering of raw
and fuel.
Carbon source is an essential factor in de novo dioxin formation.
The type, size, concentration, and structure of the carbon source
will all affect the amount of dioxin formation (Grandesso et al.,
2011). It is generally considered that the volatile organic com-
pounds (VOCs) contribute to the dioxin formation (Hoekman and
Robbins, 2012; Jeon and Jeon, 2017; Wang et al., 2003). The abil-
ity of the different forms of carbon to promote dioxin formation
is in the order of charcoal, Carbonized glucose, coal ash, graphite.
Besides, the aliphatic and aromatic functional groups can also pro-
mote the formation of dioxin (Yan et al., 2006). Compared to coke,
anthracite contains more volatile, so it is out of question that adding
the ratio of anthracite coal will increase dioxin formation in the
sintering process. Kawaguchi and Matsumura (2002) studied the
86 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
Fig. 5. Concentrations of dioxins in exhaust gas and gas temperature at each wind
box (Kasama et al., 2006a,b).
effect of different coke particle size on the formation of PCDD/Fs.
The result showed that the yield of PCDD/Fs increased almost 10-
fold over base levels with the particle size of coke decreasing from
the size 3–0.25–0.5 mm. Zhang et al. (2017) increased the car-
bon concentration from 2 to 10 wt%, the total amounts of PCDDs
and PCDFs increased from 449 pg/g-fly ash and 260 pg/g-fly ash to
much higher values of 4779 pg/g-fly ash and 3302 pg/g-fly ash, and
obtained the maximum productions at a 10 wt% carbon content.
Stieglitz et al. (1989) tested the effect of carbon concentration on
the formation of PCDD/Fs. He found that the PCDD/Fs showed a lin-
ear increase with carbon concentration increasing to 4 wt% in the
annealing process of fly ash at 300 ◦ C and then showed no further
increase. In addition, the presence of soot carbon (and also Cl) in
ironmaking and steelmaking dusts, which are recycled in sintering,
may cause the high levels of PCDD/F. Studies have shown that addi-
tion of electrostatic precipitator dust increases the emission level
of PCDD/Fs by more than three times in magnitude compared to a
case without electrostatic precipitator dust (Huang and Buekens,
1995; Nakano et al., 2009; Xhrouet and De Pauw, 2004).
4.2. Process control
Although the source reduction and terminal management can
both reduce dioxin emissions, the source reduction will increase
the demand for sintering raw material. In steel industry, the sin-
tering process shoulders the function of treating dust of the steel
mill. Without treating dust, it will cause the waste of resources.
Fig. 6. Effect of adding urea on PCDD/Fs and SO2 emission concentration (Long et al., 2012).
But adding a new dust treatment process to remove the sensitive
element in the dust will input a new cost. In addition, end treat-
ment generally requires a creation of new equipment, equipment
installation and operation will have a cost of additional investment.
Therefore, it is more convenient and economically feasible method
that changing the process conditions, adding inhibitors or using
flue gas recycling technology and other means to reduce dioxin
emission in the sintering process based on the existing sintering
equipment (Long et al., 2016a,b,c).
4.2.1. Optimum operating conditions
The dioxin formation temperature is between 250 and 500 ◦ C.
So it is possible to reduce the amount of dioxin generated by cool-
ing with advanced technology to decrease the residence time of
the flue gas at the temperature (Wu et al., 2014). The research
by Ghorishi and Altwicker (1995) shown that when the flue gas
temperature of inlet was 430 ◦ C and the outlet was 390 ◦ C, the con-
centration of dioxin in flue gas was 122.5 ng/m3 . But the flue gas
temperature of outlet became 125 ◦ C after shock cooling, the con-
centration of dioxin in flue gas was only 30.9 ng/m3 . The sintering
time also affects the generation of dioxin (Kasai et al., 2001). By
controlling the sintering time to make the sintering end located
at the sintering machine tail to reduce dioxin formation. Study by
Yang et al. (2011a, 2011b) has found that suitable sintering condi-
tions can reduce dioxin emissions. Meanwhile, the oxygen content
in the sintering atmosphere also has a complicated impact on the
formation of dioxin. On the one hand, lowering the oxygen con-
tent can inhibit the progress of the de novo reaction. So the dioxin
content is decreased with the reduction of oxygen content. On the
other hand, increasing the oxygen content can enhance the com-
bustion efficiency and reduce the concentration of organic matter
in the incomplete combustion products (Yu et al., 2012). Therefore,
choosing an appropriate oxygen concentration can reduce dioxin
formation in the sintering process.
4.2.2. Sintering exhaust gas recirculation
The exhaust gas recirculation is that the flue gas with dioxin
which is formed by sintering is put into the high temperature sin-
tered layer again to destroy the dioxin (Zhang et al., 2012). The
research has shown that flue gas recirculation not only reduces
dioxin, but also saves fuel consumption and achieves a variety
of pollutants synergistic reduction. The EOS (emission optimiza-
tion sintering) technology was used at sintering machine in Corus
steelworks, Ijmuiden, Netherlands, with 50% flue gas recycling. The
dioxin emission can reduce by 70%, particulate matter and NOx
emission also decrease by nearly 45% (Long et al., 2010; Yue et al.,
2015). After that, Siemens VAI (Voest-Alpine Industrieanlagenbau)
 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91 87

Fig. 7. Schematic diagram of ammonia radical inhibits dioxin generation (Wu et al., 2016).

Fig. 8. Schematic diagram of H radical attacking C and O atom (Okamoto, 1999).

designed the Eposint technology by further optimizing the EOS
process according to the temperature and pollutant emission char-
acteristics of the sintering machine wind box. The flue gas from part
of the high temperature wind boxes is cycled in it, which makes
Eposint process can be applied to a variety of process conditions
(Fleischander et al., 2008). The LEEP (Low emission and energy opti-
mized sintering process) developed by HKM (Hüttenwerke Krupp
Mannesmann GmbH) company employs heat exchange technol-
ogy (Yang et al., 2011a,b), which uses the exhaust gas after heat
exchanging to circle and injects activated carbon with adsorptive
action in low temperature exhaust gas. Cui and Yu (Cui et al., 2014;
Yu et al., 2012) adopted a pilot-scale equipment to study the effect
of exhaust gas recirculation on dioxin emission. The result showed
that the higher the temperature of the circulating flue gas, the more
conducive to the formation of dioxin and reducing the oxygen con-
tent of the recirculating flue gas appropriately can reduce dioxin
emission without changing the quality of the sintering.
4.2.3. Additive inhibitor
Inhibitors achieve dioxin suppression by either combining with
Cl or disrupting catalytic activity of metal catalysts. The main
inhibitors include nitrogen-containing, sulphurous and alkaline
substances. Lone pair electrons of N and S in nitrogen-containing
and sulphurous inhibitors are able to form stable complexes with
catalytic metals to retard the activity of the catalyst. Whilst, alkali
compounds and ammonia can react with HCl to reduce the chlo-
rine in synthesis of dioxin (Ismo et al., 1997). Zhang et al. (2016)
investigated the effect of different sulphur inhibitors on forma-
tion of dioxin. The results showed that calcium sulphate dehydrate
CaSO4 ·2H2 O; calcium polysulphide (CaSx); ammonium sulphate
((NH4 )2 SO4 ); 4-methylthiosemicarbazide H3 C-SC(NH)2 NH2 and
thiourea (H2 NCSNH2 ) all have a marked inhibiting effect on for-
mation of chlorobenzenes and chlorobenzenes biphenyls and the
inhibition efficiency related to the molar ratio of (S + N)/Cl.
88 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
Fig. 9. Effect of urea location on PCDD/Fs concentration of flue gas.
Although the sulphurous inhibitor can effectively inhibit the
formation of dioxin during sintering (Tuppurainen et al., 1998),
introducing sulphurous compounds into the raw sinter mix directly
will lead to a high SO2 emission level in flue gas inevitably and
increase the desulfurization burden for the iron and steel indus-
try (Ooi and Lu, 2011). Alkaline inhibitors, such as calcium oxide,
sodium hydroxide, potassium hydroxide and others have been
found to be effective as they react with hydrogen chloride to
form alkali chlorides. In the process, the chlorine is transferred to
the particle phase, thereby the chlorine element in the gas phase
is reduced. The research found that using calcium hydroxide or
sodium hydroxide can reduce efficiency of dioxin emission to 90%
(Ooi and Lu, 2011), but Na and K is not conducive to the operation
of blast furnace and lead to form a blast furnace accretion easily.
In contrast, the nitrogen-containing inhibitors have a signifi-
cant inhibitory effect on dioxins, especially the compounds contain
amine group, such as urea, melamine, ammonium hydroxide, tri-
ethylamine, ammonium hydrogen phosphate, ethanolamines and
others (Kasama et al., 2006a,b; Ooi et al., 2008a,b; Tuppurainen
et al., 1998). The mechanism of dioxin emission reduction includes
two aspects: on the one hand, the ammonia-containing material
forms a stable inert compound with the metal catalyst to weaken
or eliminate the catalytic activity of the metal and its oxides. On
the other hand, NH3 produced from thermal decomposition of
ammonia-containing substances react with HCl to reduce the chlo-
rine source of deacon reaction.
Southern was the first to succeed in suppressing the emission
of dioxin from sintering plants by adding urea to the raw mixture
(Nakano et al., 2005). Addition of 0.02% and 0.025% urea in raw sin-
ter mixtures reduced PCDD/F emissions by about 50–60% (Southern
et al., 2000). Ooi et al. (2008a,b) studied the organic dioxin suppres-
sants (urea and melamine) were added into raw sinter mix to inhibit
the formation of dioxin. Urea was added at a concentration of 0.02%
of the raw sinter mix and Melamine was used at five different addi-
tion rates viz., 0.005%, 0.01%, 0.015%, 0.02% and 0.05% of the raw
sinter mix. The results shown that the addition of solid urea resulted
in 54% suppression of PCDD/F emissions and the highest level of
PCDD/F reduction was attained with 0.015% melamine, whereby
PCDD/F formation was reduced by 64%. Anderson et al. (2007) used
solid urea, aqueous urea and monoethanolamine (MEA) as reagents
for the suppression of PCDD/Fs in the iron ore sintering process.
The addition of solid urea, aqueous urea or MEA, at 0.009% nitro-
gen equivalent (0.02% urea or 0.042% MEA), reduced the formation
of total PCDD/Fs, targeted PCDD/Fs and PCDD/F I-TEQ by 47–53%,
62–64% and 59–62%, respectively.
Fig. 10. Schematic diagram of urea location in T3.
Our laboratory also reported that trace amount of urea was
added in the sintering mixture can significantly reduce the for-
mation of dioxin during the sintering process and also have the
effect on desulfurization (Long et al., 2012, 2016a,b,c; Qian et al.,
2016; Wu et al., 2016). As shown in Fig. 6, when the addition of
0.05%, 0.1%, 0.5% urea, the dioxin suppression efficiency was 63.26%,
66.78% and 71.98% respectively, and the emission concentration
of SO2 was significantly decreased. For dioxin, the mechanism of
emission reduction is that the urea and its decomposition products
occupy the active site of the catalyst surface and form a stable inert
compound with the metal catalyst (such as copper) to weaken or
eliminate the catalytic activity of the metal and its oxides.
The NH2 active group and hydrogen radical (H• ) are formed
directly in the pyrolysis process of urea. They are an important part
that urea inhibits the dioxin formation. As shown in Fig. 7, the NH2
group produced by the decomposition of urea can react with the
carbon atoms at the edge active sites on the surface of the fly ash by
replacing the functional groups. So the organic compounds that to
be synthesized into dioxin are converted into nitrogen-containing
organic compounds of similar structure, thereby the toxicity and
hazards of persistent organic matter in flue gas are reduced (Kasai
et al., 2008; Wu et al., 2016).
The hydrogen radical has a strong activity as shown in Fig. 8. It
can attack the carbon and oxygen atoms of C O bond in the dioxin
molecules to make the C O bond of dioxin broken (Fueno et al.,
2002; Okamoto, 1999). At the same time, NH2 groups can combine
with hydrogen radical to form NH3 . The NH3 and Cl2 that formed by
the reaction in the preheating and drying zone undergo a reduction
reaction to form HCl. Then the NH3 react again with HCl to form
NH4 Cl to inhibit the Deacon reaction, thereby the dioxin emission
reduction in iron ore sintering process is achieved.
In addition, in our recent study, we used a commercial sinter-
ing plant’s raw materials to finish three groups sinter pot test. The
results are shown in Fig. 9. The sample of T1 was a reference period
without urea, the sample of T2 was experimental periods with
0.035 wt% solid urea added directly in the granulating process and
the sample of T3 is also experimental periods with 0.035 wt% solid
urea placed at a distance from the sintering grate bar of 100 mm
height, as shown in Fig. 10.
Fig. 9 showed the discharge concentration of dioxin without
urea is 0.5 ng-TEQ/m3 , with adding 0.035 wt% urea added in the
granulating process or at a distance of 100 mm height, them were
0.12 and 0.15 ng-TEQ/m3 respectively. So if the dioxin formed in
drying and preheating zone is not decomposed as the flame front
moved down, it is transferred to the lower part of layer with wet
zone, dioxin concentration will be more and more in wet zone.
When the wet zone gets to the layer with urea, urea can’t destroy
the dioxin molecular structure, who has formed. So, when the
 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
Fig. 11. Schematic image describing the release of exhaust gas components (Kasama et al., 2006a,b).
drying zone begins to reach the grate surface, the dioxin will be
discharged into exhaust gas. But the result is not the case.
Kasama et al. (2006a,b) analyzed the dioxin emission of wind
boxes exhaust gas at the Oita No. 1 sintering bed, as shown in Fig. 11.
PCDDs and PCDFs release into exhaust gas were confirmed in two
stages and the second stage was the main emission areas where
the high temperature zone has reached the hearth layer. In other
wind boxes PCDDs and PCDFs emission concentration is not high.
When the drying zone begins to reach the gratesurface, the wet
zone almost disappears, but the PCDDs and PCDFs emission con-
centration is still low. So Kasama inferred that the second stage
PCDDs and PCDFs might have been produced in the wind boxes,
with organic substances and chlorine supplied from incompletely
sintered areas or with grease and dust in the wind boxes. Therefore,
the dioxin, who is mainly generated in the dry zone, may not be
transferred to the wet zone during sintering process and released
into the exhaust gas with the wet zone disappeared. So it can be
speculated that the dioxin formed in drying and preheating zone
is transferred to the lower part of the material layer which would
be a chemical transfer process. I.e., the dioxin formed in drying
and preheating zone might be absorbed on porous materials and
be pyrolyzed by the next high temperature process, and then the
decomposition is transported to the wet zone. When the temper-
ature of wet zone reaches 250–500 ◦ C, the dioxin is formed again
(Long et al., 2016a,b,c).
4.3. End treatment
End treatment is a method of treating dioxin that has been
formed in the sintered flue gas. Usually, the dioxin in sintered flue
gas are in the form of gas phase and particulate phase. In theory,
the particulate phase dioxin can be removed in large quantities by
cyclone separator, bag filter and electrostatic precipitator, while
the dioxin in gas phase is removed by activated carbon adsorption
and selective reduction with contact.
The de novo synthesis of dioxin occurs mainly on the surface of
fly ash during the sintering process (Stieglitz and Vogg, 1987; Vogg
et al., 1987), so a large number of dioxins stay on the surface of fly
ash. Furthermore, the fine particles in the flue gas have larger spe-
cific surface area, which easier to adsorb dioxin and other gaseous
pollutants. And the smaller the size of particle, the stronger the
adsorption capacity. So the dioxin can be reduced by removing the
89
fly ash of flue gas efficiently. Bag filter and electrostatic precipi-
tator have a high efficiency of dust removal in flue gas generally.
Therefore, they also have commendable effect on dioxin emission
reduction while removing particulates in flue gas. But there is no
significant effect on the dioxin in gas phase.
The SCR (selective catalytic reduction) (Dhanushkodi et al.,
2008) method is that adding a catalyst device after the sintering
wind boxes (such as the oxide of V, Ti, W), then the flue gas with
dioxin flows through the surface of catalyst. Dioxin is oxidized at
a low temperature by oxygen to produce inorganic matter such as
CO2 , water, HCl and others. Finally, these decomposition products
re-enter the exhaust pipe. A study by Goemans (Goemans et al.,
2004) has shown that SCR reactor has a significant catalytic degra-
dation effect on dioxin in both gas and particulate phases, and the
total rate of dioxin emission reduction is 85%.
Activated carbon has a large specific surface area, which can
effectively adsorb dioxin, and this is also one of the important
method of dioxin reduction at present. Hung et al. (2011) has shown
that the activated carbon can adsorb dioxin in the gas phase and
particulate phase when its powder is sprayed upwards into the
bag filter. With the activated carbon that adsorbed dioxin is fil-
tered down from the bag filter, the removal rate of dioxin is more
than 95%. In China, TISCO (Li, 2013) adopted the dry desulfuriza-
tion & denitration system of sinter flue gas, the physical adsorption
and dust collection of active carbon were used to remove diox-
ins at the same time. The dioxin removal rate was up to 98.5%.
But this method exists a disadvantage that it is likely to cause sec-
ondary pollution, if the activated carbon after adsorbing dioxin is
not re-treated or buried as a dangerous article.
Because of dust removal technology of sintering flue gas and
adsorption technology of activated carbon just achieve the transfer
of dioxin emissions, they do not reduce the total amount of dioxin
in the environment fundamentally.
5. Conclusions
(1) The technology of dioxin emission reduction in sintering
exhaust gas has just started in China. With the national envi-
ronmental policy continues to intensify, the suitable solutions
should be urgently found from the technical and economic
point to achieve the dioxin emission reduction. In addition, the
90 L. Qian et al. / Process Safety and Environmental Protection 117 (2018) 82–91
dioxin-like compounds including polychlorinated biphenyles,
chlorobenzenes and polychlorinated naphthalenes have also
been detected from iron ore sintering plants. Thus, the syner-
getic control of dioxins and dioxin-like compounds could be
significant and might be an important aspect for future pollu-
tion control during the sintering.
(2) In the dioxin emission reduction technology of iron ore sinter-
ing, the source control technology has a strict demand for raw
materials, which will increase the cost of raw materials pro-
curement undoubtedly, and the investment and operating costs
of end treatment are high. While the process control technol-
ogy has the advantages of simple process, low investment and
low running cost, which is expected to be an important devel-
opment direction for the future emission of dioxin in iron ore
sintering.
Acknowledgments
This work was supported by the Key Program of National Natural
Science Foundation of China (U1660206), the Programs of National
Natural Science Foundation of China (51674002 and 51504003).
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