Journal of Cleaner Production 298 (2021) 126788

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Journal of Cleaner Production

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

Review

Pyrometallurgical recovery of zinc and valuable metals from electric

arc furnace dust e A review
Jie Wang a, Yingyi Zhang a, b, *, Kunkun Cui a, Tao Fu a, Jianjun Gao c, Shahid Hussain d,
Tahani Saad AlGarni e
a
School of Metallurgical Engineering, Anhui University of Technology, Maanshan 243002, Anhui Province, China
b
College of Material Science and Engineering, Chongqing University, Chongqing 400030, PR China
c
State Key Laboratory of Advance Steel Processes and Products, Central Iron and Steel Research Institute, Beijing 100081, China
d
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, PR China
e
Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

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

Article history: Electric arc furnace dust (EAFD) has attracted more and more attention as a kind of metallurgical solid
Received 27 December 2020 waste with huge production. How to reduce its harm to the environment and efficiently recover valuable
Received in revised form metals such as zinc, lead and iron from its complex components to realize the comprehensive utilization
17 March 2021
of EAFD is the aim of various EAFD treatment processes. In this paper, the physical and chemical
Accepted 18 March 2021
Available online 23 March 2021
properties of EAFD are discussed from the micro and macro perspectives, the microstructure, chemical
composition and phase composition of EAFD in various countries are summarized in detail. According to
Handling Editor: Prof. Jiri Jaromir Kleme
s the zinc content, EAFD can be divided into three types: high-zinc, medium-zinc and low-zinc. The results
show that Fe, Ni, Cr and other elements increase with the decrease of zinc content in EAFD. Not only the
Keywords: zinc oxide but also abundant FeeNieCr alloy of high value can be recycled from the low-zinc EAFD,
Electric arc furnace dust which provides guidance for EAFD treatment. At the same time, the general mechanism of direct
Pyrometallurgy reduction and smelting reduction pyrometallurgical processes of EAFD is expounded, and the existing
Recovery pyrometallurgical processes such as rotary kiln process, rotary hearth furnace process, Primus process,
ZnO
ESRF process and Coke-packed bed process are summarized and compared from the aspects of energy
FeeNieCr alloy
consumption, production capacity, process flow to actual application status. In addition, the properties of
Characterization
directly reduced iron and zinc-rich dust obtained by pyrometallurgical processes of EAFD are also dis-
cussed. Finally, a new process of treating EAFD by combining direct reduction process and smelting
reduction process is proposed to overcome the defects existing in two types of pyrometallurgical pro-
cesses, and the development of preparing zinc oxide micropowder and high valued FeeNieCr alloy by
pyrometallurgical process of EAFD is prospected.
© 2021 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Microstructure and properties of EAFD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Generation mechanism of EAFD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Physical properties and microstructure of EAFD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Chemical composition and phase composition of EAFD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Mechanism and process of pyrometallurgical process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Reaction mechanism of pyrometallurgical process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. General situation of pyrometallurgical process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.1. Rotary kiln process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

* Corresponding author. School of Metallurgical Engineering, Anhui University of

Technology, Maanshan 243002, Anhui Province, China.
E-mail address: [email protected] (Y. Zhang).

https://doi.org/10.1016/j.jclepro.2021.126788
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

3.2.2. Rotary hearth furnace (RHF) process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

3.2.3. PRIMUS process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.4. Electric smelting reduction furnace (ESRF) process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.5. Coke-packed bed process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4. Characterization of EAFD products treated by pyrometallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.1. Characteristics of direct reduced iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.2. Characteristics of zinc-rich dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5. Conclusion and prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Author contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

1. Introduction the largest source of secondary zinc resources, the utilization rate of
EAFD to zinc is lower than that of other secondary zinc containing
Steel production is an important index to measure the national resources, so there is still a long way to go in the full recovery of
economic strength. Using the scrap steel as the main raw material EAFD. It is estimated that 70% of the world’s Zinc comes from zinc
and electricity as the energy source, the short-process electric arc ore smelting, and 30% of the world’s Zinc comes from the recovery
furnace (EAF) steelmaking has become one of the main steelmaking and comprehensive utilization of secondary zinc resources (Kaya
methods in the world (Jaimes and Maroufi, 2020). At present, EAF et al., 2020). According to statistics, the output value of China’s
steel production has accounted for more than 30% of the global secondary zinc in 2015 was about 25 billion yuan. U.S. Recycled zinc
steel production. In many developed countries, the proportion of production accounts for more than 50% of the total zinc production,
EAF steelmaking has even reached 80% due to the sufficient scrap and its utilization of secondary zinc resources is at the world’s
resources. Electric arc furnace dust (EAFD) is one of the main by- leading level. What’ s more, developed countries such as the Europe
products of EAF steelmaking. Every 1t steel produced by EAF will and Japan are actively encouraging the use of zinc secondary ma-
produce 10e20 kg EAFD (Stefanova et al., 2015). Due to its small terials to produce zinc.
particle size and heavy metal elements such as Pb, Cr and Cd. The In 2000, China’s zinc consumption of 1.4 million tons has sur-
EAFD is listed as hazardous waste from specific source, K061, ac- passed that of the United States, becoming the world’s largest zinc
cording to ABNT 10004:2004 (de Araujo and Schalch, 2014). Studies consumer. By 2014 this figure had more than quadrupled, with 6.42
by Adamson (2000) and Valavanidis et al. (2008) also show that air million tons of zinc consumption accounting for 47% of the world’s
pollution caused by EAFD particles is able to cause cancer. However, total (Guo et al., 2010). However, the proportion of recycled zinc in
the EAFD contains a large amount of valuable metal elements such China is only 11%, which is much lower than the level of recycled
as Fe, Zn and others, which are of high recycling value. EAFD, hot zinc in the United States (Yan et al., 2013), and a large amount of
galvanizing slag/ash, scrap zinc alloy and zinc material, gas mud/ zinc alloy, zinc concentrate and refined zinc need to be imported
ash, zinc-containing dust generated in copper and lead smelting every year. With the production and utilization of zinc-containing
process, and zinc waste generated in the generation process of a secondary resources shown in Fig. 1 (b), it can be seen that the
small amount of zinc alloy are collectively referred to as secondary largest source of renewable zinc resources in China is 0.93 million
zinc resources. Fig. 1 (a) shows the current situation of the world’s tons of hot galvanizing slag/ash, accounting for 38.9% of the total, of
secondary zinc resources in 2015. It can be seen that the total which 0.24 million tons of EAFD exist, accounting for 10% of the
amount of the global secondary zinc resources was 5.72 million total, and 4.6% of zinc resources comes from imported zinc-
tons, and the total utilization of resources was 3.86 million tons. containing materials. Compared with the global production of 2
The total output of EAFD was 2 million tons, accounting for 35% of million tons of EAFD in the same period, the gap of the total amount
the total amount of zinc containing waste. EAFD was the largest and utilization rate of EAFD between China and the global level is
source of secondary zinc resources, followed by hot-dip galvanized still large. Worse still, the utilization rate of EAFD in many steel
slag/ash, with a total amount of about 1.68 million tons, accounting plants is less than 20%. Because of the poor economic effect, many
for 29% of the total zinc waste. However, the utilization rate of hot- steel enterprises choose to bury or ignore it, resulting in a large
dip galvanizing slag/ash is 83%, while that of EAFD is only 60%. As amount of EAFD piling up but still neglected.

Fig. 1. Generation and utilization of zinc-containing secondary resources. (a): Worldwide; (b): In China (2015).

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

According to the statistics of China Scrap Iron and Steel Appli- processes are summarized too. In addition, we have also compared
cation Association, the total amount of scrap steel resources in the advantages and disadvantages of various pyrometallurgical
China will reach 290 million tons by 2025. As EAF steelmaking is processes and elaborated the countermeasures, aiming at providing
the best way to deal with these large amounts of scrap steel, the useful guidance for the secondary utilization of EAFD and the
output of EAF steel will increase greatly in the future, and the sustainable development of zinc resources.
accompanying EAFD will also be produced and stored in large
quantities. The situation of secondary zinc resources in China will 2. Microstructure and properties of EAFD
be in line with that of the global secondary zinc resources. EAFD
will gradually become the largest source of secondary zinc re- 2.1. Generation mechanism of EAFD
sources in China. EAFD as a solid waste rich in valuable metals, will
not only causes waste of resources, but also seriously endangers the EAFD is one of the main by-products in EAF steelmaking, and its
environment if it is not effectively treated in time. The market formation is closely related to five links of EAF steelmaking: furnace
potential of EAFD recycling is remarkable. charging, melting, refining, slag foaming and casting (Gue zennec
At present, the research on the treatment methods of EAFD et al., 2005). Research shows that the splashing of steel slag and
mainly focuses on pyrometallurgical process and hydrometallur- molten steel caused by the rupture of CO bubbles on the surface is
gical process (Bakkar, 2014; Chairaksa-Fujimoto et al., 2016; Pickles, the main reason for the formation of EAFD (Han and Holappa,
2009a; Su et al., 2017; Yu et al., 2015). Hydrometallurgical process 2003). According to the research of Wang et al. (2018), the bubble
uses various leaching solutions, separates metal zinc from the rupture process can be divided into three steps, which produce two
mixture, purifies the leaching solution, and then obtains metal zinc types of droplets. Fig. 2 is a schematic diagram of the internal
ingots through electrode reaction after melting cathodic deposits. composition of the electric arc furnace and the mechanism of
According to different leaching agents, it can be divided into acid forming EAFD by the rupture of bubbles on the melt surface. As can
leaching method, alkali leaching method and ammonia leaching be seen from Fig. 2 (a), with the CO bubbles generated by smelting
method (Canbekte, 2015; Gargul and Boryczko, 2015; Halli et al., gradually rising, the covered liquid phase layer becomes thinner
2018; Zhang et al., 2019). Its advantages are lower equipment in- and thinner near the gas-liquid intersection interface. As Fig. 2 (b)
vestment and lower energy consumption. However, the hydro- shows, when the melt film covering the bubble reaches the critical
metallurgical process equipment is easy to be corroded (Zhao and thickness, the CO bubble will burst, which causes the melt film
Stanforth, 2000a), and a large amount of metallic iron in leaching expand and break into small liquid droplets. The droplets formed in
residue cannot be fully recovered and utilized, with toxic wastes this way are called thin film droplets, and the similar steel slag
remained (Tom as et al., 2006), such as Cd, PbSO4, PbCO3, etc. In composition in the EAFD benefits from this formation method.
addition, Zn in EAFD is mainly exist in the form of zinc ferrite Many researchers believe that the size of thin film droplets is
(ZnFe2O4) and zinc oxide (ZnO) (about 20e50 wt% of Zn forms related to the size of bubbles, and the number of droplets is related
ZnFe2O4) (Olivieri and Veglio  , 2007), while ZnFe2O4 is more stable to the area of thin film (Emery et al., 2018). The particles size of
than ZnO and difficult to be dissolved, which results in low recovery EAFD formed by such droplets are between 0.3 and 500 mm. The
rate. concave place occupied by the broken bubbles still exists until the
Compared with hydrometallurgical process recovery of EAFD, liquid is filled, which will generate an upward jet. The melt at top of
pyrometallurgical process is more widely used, which utilizes the the jet will decompose into liquid droplets. This kind of droplets
properties of low boiling point and easy volatilization at high called jet droplets, as shown in Fig. 2 (c). Due to the large size of jet
temperature of zinc and lead, volatilizes and re-enriches zinc and droplets, they will not enter the dust collection system with the
lead contained in dust through reduction reaction. The process of discharge of furnace gas. Therefore, zinc-containing EAFD is mainly
pyrometallurgical recycling of EAFD can be divided into direct caused by splashing of thin film droplets, which also leads to the
reduction and smelting reduction according to different process small size of zinc-containing EAFD.
conditions (Stewart et al., 2020). Coal-based direct reduction pro- While the metal vapours generated in the furnace mainly forms
cess for EAFD treatment (rotary hearth furnace process and rotary EAFD by two mechanisms. The first mechanism is called
kiln process) is considered to be the most mature pyrometallurgical
process at present, due to its low reduction temperature and simple
operation flow. However, the thermal efficiency of the coal-based
direct reduction process of the rotary hearth furnace and the ro-
tary kiln is very low, and the ring formation problem (Collision,
extrusion and local overheating cause overproduction of the liquid
phase of the granular material, which tend to stick to the kiln’s wall
and to form hard rings.) also limits the development of the rotary
kiln process to a certain extent (Zhang et al., 2020). And smelting
reduction process also faces severe technical challenges in smelting
equipment and process, due to its high smelting temperature and
smelting intensity (Zhang et al., 2019b), such as refractory erosion
and top gas utilization.
Although there are various problems in the industrial applica-
tion of pyrometallurgical process of EAFD, pyrometallurgical pro-
cess still has high economic benefits in recovering direct reduction
iron (DRI), zinc-rich dust and ferroalloy. In this work, the genera-
tion mechanism, physical and chemical properties, microstructure
and phase composition of EAFD are discussed in detail. The tech-
nical characteristics and challenges of several pyrometallurgical Fig. 2. Schematic diagram of an electric arc furnace and the burst of bubble on liquid
processes for treating EAFD are summarized, and the characteris- surface in it. (a): Bubble emerging at the liquid surface; (b): Rupture of the liquid film;
tics of zinc-rich dust and ferroalloy obtained by pyrometallurgical (c): Formation of liquid jet and droplets.

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

heterogeneous nucleation deposition, i.e., volatile metal deposition size distribution, as shown in Fig. 4 (a), the left axis is the frequency
on the surface of solid particles, and most metal deposition is car- curve of particle size distribution, and the right axis is the cumu-
ried out in this way (Loaiza et al., 2017). Under the action of elec- lative curve of particle size composition. Two obvious peaks can be
trostatic attraction, smaller particles in furnace dust gradually seen from the frequency curve of particle size distribution, indi-
gather into larger particles with a diameter of 200 mm. The second cating that there are two main particle size distribution intervals for
mechanism is called homogeneous nucleation and growth. When the sample. It can be seen from the figure that 90% of the particles
there are not enough solid particles to agglomerate in the first are less than 4.771 mm, 50% are less than 0.77 mm, 10% are less than
mechanism, the volatile metal completes initial growth through 0.156 mm, and the average particle size of the EAFD sample particles
collision and adhesion between gas phase substances. When the is 0.77 mm. Oustadakis et al. (2010) used a similar method to study
particles grow up to 0.02e100 mm, dust is formed by mechanical the particle size of EAFD samples, and also found a phenomenon of
agglomeration according to the first mechanism. Research shows bimodal particle size distribution, as shown in Fig. 4 (b). The two
that, as the electric arc furnace is rapidly heated to 1600
C main particle size intervals are (0.1e1 mm) and (1e100 mm)
panes Robau et al., 2001), oxides in the slag mixed with metal
(Ta respectively. A similar conclusion was found in the research
vapours and furnace dust are carried out of the furnace by the rising conclusion of Xanthopoulos et al. (2017). Their experimental results
hot gas flow, and then enter the flue along with the gas flow to be show that there are also two main particle size intervals of EAFD,
oxidized, vulcanized or chlorinated in the dust collection system, which are (0.1e1 mm) and (>7 mm) respectively.
finally forming EAFD to be collected in bag dust collector, gravity or Fig. 5 shows typical micrographs of EAFD. As can be seen from
electrostatic dust collector. Fig. 5 (a), the particle size of EAFD is small, some large particles of
EAFD are also observed (Pickles, 2009b). These large particles may
2.2. Physical properties and microstructure of EAFD be that the small liquid droplets ejected from liquid metal and slag
in the EAF smelting process are oxidized while being used as the
Typical EAFD has a reddish brown or dark brown appearance, settling core of gas phase metal in the rising process, and finally
very fine particles, and can propagate in the air (Ma et al., 2006a). form large particles of EAFD by heterogeneous nucleation mecha-
Due to the difference of EAF steelmaking process and collection nism (da Silva et al., 2008). A similar conjecture was proved in the
methods, the physical characteristics of EAFD will change within a research of Kelebek et al. (2004). As shown in Fig. 5 (b), the sliced
certain range. Taking the particle size of EAFD as an example, there zinc-containing converter slag particles were characterized by
are obvious differences in particle size of EAFD obtained by SEM-EDX, the results show that the large particles are composed of
different dust collection methods. According to the statistics in the internal iron core, middle iron oxide layer and outermost zinc
existing literatures, three main particle size intervals are found ferrite layer, which conforms to the assumption of heterogeneous
(85% particle size < 10 mm (Grillo et al., 2014), 90% particle nucleation. In addition, attractive binding between the particles
size < 50 mm (Kukurugya et al., 2015), more than 90% particle may occur, eventually forming larger aggregates (Mostafa et al.,
size < 100 mm (Martins et al., 2008)). Generally, the average particle 2018). Research shows that the particle size distribution of EAFD
size of EAFD collected by gravity dust removal is the largest, fol- is closely related to its moisture content, and the particles will also
lowed by that collected by bag dust removal, and the average coagulate through water and reaction. Long-term storage will lead
particle size of EAFD collected by electrostatic dust removal process to large particle size aggregates in EAFD (Zhang and Hong, 2011).
is the smallest. Besides the magnetism (Kul et al., 2015) and surface charge (Pickles
There is still a large amount of EAFD needs to be solved urgently and Marzoughi, 2019) of EAFD particles are also the main influ-
in the world, which accumulated around steel mills without recy- encing factors in the agglomeration process. These researches
cling or harmless treatment. Fig. 3 (a) is an EAFD mountain explain the reason why the particles size of dust varies greatly in
generated by EAF steelmaking in an Egyptian steel mill (Khattab different research. In order to further study the particle character-
et al., 2017). Fig. 3 (b) shows the Scanning Electron Microscope istics of EAFD,Lee and Song (2007) took SEM microscopic
(SEM) images of EAFD of a steel plant in Saudi Arabia, Dhahran morphology photos of EAFD collected by bag dust removal in a steel
31261, Saudi Arabia, which was taken by Massarweh et al. (2020). It mill in South Korea as shown in Fig. 5 (c). Research shows that
can be seen that EAFD mainly composed of small particles and except about 8% of the dust particles have particle size exceeding
aggregates, which may correspond to multiple major particle size 9 mm, the rest are all below 10 mm, and the median particle size is
intervals of EAFD. calculated to be 1.07 mm. This result is consistent with the research
Silva et al. (2019) measured the particle size of EAFD with laser results of Mantovani et al. (2013), the dust particle size is usually
particle size analyzer and gave the statistical results of its particle between 0.1 and 10 mm, and researchers believe that particles with

Fig. 3. Macroscopic and microscopic morphology of EAFD. (a): Real size picture (Ma et al., 2006a); (b): SEM image of EAFD (Massarweh et al., 2020).

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 4. Particle size distribution according of EAFD. (a): (Silva et al., 2019); (b): (Oustadakis et al., 2010).

Fig. 5. The micro appearance of EAFD. (a): SEM photographs of the dust (Pickles, 2009b); (b): Cross-sectional composition of a spherical particle from BOF sludge (Kelebek et al.,
2004); (c): SEM photographs of the dust (Lee and Song, 2007); (d): TEM images of the EAFD (Khattab et al., 2017).

particle size greater than 10 mm can be regarded as particle ag- of scrap steel, the process conditions and the recycling degree of
gregates formed by a single EAFD particle. Similarly, Khattab et al. EAFD (Simonyan et al., 2019). At present, according to the different
(2017) used a higher power electron microscope to photograph zinc concentration in EAFD, it can be divided into three types: low-
EAFD from an Egyptian steel mill, as shown in Fig. 5 (d). The zinc (Zn < 8 wt%), medium-zinc (8 wt% < Zn < 20 wt%) and high-
microstructure of single EAFD particles was observed by TEM zinc (Zn > 20 wt%) (Sikalidis et al., 2010). The main reason for the
detection. It can be seen that the morphology of the particles is enrichment of zinc content in EAFD is to use scrap steel with high-
mostly spherical, and the diameter of spherical particles is between zinc content for EAF smelting (Lanzerstorfer, 2018). In addition, in
20 nm and 2 mm. The shape of single particles is relatively regular order to recover the metal iron in the EAFD, a large amount of EAFD
and the distribution is relatively uniform. The physical character- is added to the EAF scrap steel smelting as secondary resources
istics of the EAFD are directly or indirectly determined by the after being lumped, which eventually leads to the enrichment of
structural characteristics of the EAFD. zinc content in the EAFD (Lo  pez et al., 2002).
The physical properties of EAFD have certain guiding effects on In order to investigate the chemical composition of EAFD, a large
its storage, transportation and recovery process. In addition to the number of studies have been carried out. Table 2 shows the
granularity of the particles, other physical properties such as den- chemical composition of different types of EAFD. It can be seen that
sity, specific surface and solubility of EAFD are summarized in the content of zinc in all kinds of EAFD varies greatly, while the
Table 1. It can be seen that the specific surface area of dust varies content of iron varies slightly. High-zinc and medium-zinc EAFD
greatly detected by different researchers, with the specific surface have high-zinc content and relatively low iron content. The zinc
area varying from 0.15 to 4.82 m2 g1. However, the density of dust content of high-zinc EAFD is about 20e27 wt%, the iron content is
varies slightly, usually between 1.10 and 5.52 g cm3, which is about 17e40 wt%, and the average content of iron element is
mainly due to the change of dust particle size. The finer particle size 27.4 wt%. The zinc content of medium-zinc EAFD is about 12e20 wt
and larger specific surface area of EAFD materials correspond to %, the iron content is about 16e40 wt%, and the average iron con-
better performance in the pelletizing and block-making processes, tent is 29.7 wt%. In addition, high and medium-zinc EAFD also
and the pellet strength will also be higher (Montenegro et al., 2016). contains a certain amount of heavy metal elements such as Pb, Cd,
In addition, it can be seen from the table that the solubility of EAFD Cu, and a small amount of valuable metal elements such as Ni and
in water is less than 10% and the pH value of the water-soluble part Cr, besides a relatively high number of Mn (1.03e3.31 wt%) is
is distributed from 4.97 to 12.42. Higher water solubility means that included. Compared with high-zinc and medium-zinc EAFD, the
the EAFD has better adhesion after adding water. The higher water zinc content in low-zinc EAFD is very low, which is only 0.07 to
solubility of EAFD, the easier pelletizing and agglomeration, and the 5.2 wt%, and Mn element is not detected. However, the iron content
higher strength of the pellets. The pH of the soluble part of EAFD is in low-zinc EAFD is relatively high, with the iron content ranging
the best at about 7, because too high acidity or alkalinity is easy to from 20 to 50 wt%, and the average iron content is about 29.0 wt%. It
cause equipment corrosion and accelerate equipment aging. is not difficult to see that with the decrease of zinc content, the iron
content increases, and the iron resources in low-zinc EAFD are
2.3. Chemical composition and phase composition of EAFD more abundant. In addition, compared with high-zinc and
medium-zinc EAFD, low-zinc EAFD also contains relatively higher
The chemical composition of EAFD mainly depends on the types Cr and Ni elements. Particularly, the research results of Tang et al.

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Table 1
EAFD physical characteristics.

Parameter Value Reference

Density(g$cm3) 1.10e2.50 Buzin et al. (2017)

3.00e3.30 Cheng (2003)
3.81 Barreneche et al. (2013)
4.08 Souza et al. (2010)
4.23 de Vargas et al. (2006)
4.30 Guray and Vedat (2008)
1.85e4.33 Fedorko et al. (2012)
3.01e5.22 Nolasco-Sobrinho et al. (2003)
Particle size distribution and Mean particle diameter 85% < 10 mm Grillo et al. (2014)
90% < 50 mm Kukurugya et al. (2015)
50% < 19 mm, 90% < 100 mm Machado et al. (2006)
50% < 2.2 mm, 90% < 20 mm Sar et al. (2019)
Specific surface area(m2$g1) 0.73 Laforest and Duchesne (2006)
4.01 Niubo et al. (2009)
4.6 Xia and Picklesi (2000)
0.15e4.82 Salihoglu and Pinarli (2008)
Water soluble fraction (wt.%) leached in water (pH) 6.7 Al-Zaid et al. (1997)
10.95 Wu and Themelis (1992)
7e8 Ledesma et al. (2018)
4.97e12.42 Stegemann et al. (2000)
10e11 Omran and Fabritius (2017)
Solubility (in water) <10% Antrekowitsch et al. (2008)

Table 2
Chemical composition (wt.%) of EAFD from different sources.

Type Zn Fe Pb Cr Al Cd Cu Ni Mn Reference

High-zinc 26.66 16.93 2.71 0.12 0.59 0.044 0.25 0.013 1.19 Al-harahsheh et al. (2014)
24.80 32.00 1.84 e 1.03 0.03 0.02 e 3.31 Zhao and Stanforth (2000b)
23.51 39.20 4.57 0.3 0.3 0.01 0.34 0.04 e Arnold et al. (2017)
22.00 22.7 4.16 e 0.67 0.061 0.25 e e Baik and Fray (2000)
Medium-zinc 19.40 24.60 4.5 0.3 e 0.1 0.42 e 2.2 Caravaca et al. (1994)
19.02 30.0 0.99 0.34 0.53 0.04 e e e Nezhad and Zabett (2016)
17.05 27.23 1.28 0.81 e 0.9 e 0.0 1.03 Laubertova et al. (2020)
12.20 37.08 1.72 0.22 0.41 0.01 0.17 e e Lenz and Martins (2007)
Low-zinc 5.20 19.37 1.4 10.9 0.39 e e 4.1 e Guylaine and Jose e (2006)
4.11 22.01 0.36 9.99 0.21 e e 2.2 e Ma and Garbers-Craig (2009)
3.75 48.58 1.02 0.22 0.20 0.01 0.22 e e Sofili
c et al. (2004)
0.77 35.88 0.28 11.15 0.34 e e 5.26 e Tang et al. (2008)

(2008) show that the content of Cr and Ni in low-zinc EAFD (zinc of EAFD are different, and the corresponding mineral composition
content is 0.07 wt%) is as high as 11.15 wt% and 5.26 wt%, respec- is also different to some extent. For example, there are a large
tively. Usually, high-zinc EAFD is preferentially used as raw material amount of zinc ferrite, iron oxide and zinc oxide in medium-zinc
in the process of recovering EAFD to ensure the economic benefits and high-zinc EAFD. However, there is very little zinc oxide in
of production. However, if the valuable metal elements such as Fe, low-zinc EAFD, and the mineralogical composition of EAFD is also a
Cr, Ni in low-zinc furnace dust are recovered in the form of alloys, complicated problem. Using “FactSage 7.2” thermodynamic soft-
the added value of recovered products will be greatly increased. ware, we simulated the phase transformation of ZneFeeCOeCO2
Machado et al. (2006) studied a medium-zinc EAFD (Zn content system under 1100
C in reducing atmosphere, as shown in Fig. 7
of 9.24 wt%) from a steel plant in southern Brazil by microscopic (a). It can be seen that with the increase of CO2 and the decrease
analysis. Fig. 6 (a) shows the secondary electron SEM image of the of CO in the system, Zn and Fe gradually form ZnO and FeO. When
EAFD, and Fig. 6(bei) show the X-ray diagrams of the EAFD. From the partial pressure ratio P(CO2)/P(CO) continues to increase to the
Fig. 6 (d), it can be seen that oxygen element is distributed in the triangular region in the upper left corner of the phase diagram, the
whole scanning area, which indicates that there is a large amount main phases of ZneFeeCO2 system are ZnFe2O4 and Fe2O3. On the
of metal oxides in the sample, while iron, zinc and oxygen elements contrary, in order to reduce metal iron at this temperature, it is
overlapping areas were observed from Fig. 6 (b), (c) and (d), which necessary to control the partial pressure ratio P(CO2)/P(CO) < 0.32
may correspond to ZnFe2O4 phase in the EAFD. The octahedral in the system. When the partial pressure ratio P(CO2)/P(CO) < 0.11,
crystals of typical spinel structure phase have been found in the zinc oxide is reduced to zinc vapour. It is a remarkable fact that
characterization results of EAFD samples by many scholars (Yadav when the partial pressure ratio P(CO2)/P(CO) continues to decrease
et al., 2018), which also proves the fact that ZnFe2O4 phase exists to the trapezoidal region in the lower right corner of the phase
in large quantities in EAFD (Zhang et al., 2012). In addition, a small diagram, gas carburizing may also occur.
amount of Ca, Cr, Si, Mg and Mn elements can also be observed in The mineralogical structure of EAFD can be accurately analyzed
Fig. 6 (e), (f), (g), (h) and (i). These detected metal and nonmetal by thermogravimetric analysis, X-ray Photoelectron Spectroscopy
elements reflect the complex elemental composition of EAFD to (XPS), X-Ray Diffraction (XRD) and SEM. Fig. 7 (b) shows the XRD
some extent. diagram of typical EAFD samples (Vieira et al., 2013). From the di-
The elements concentration and composition of different types agram, we can see that the crystal phases with the most contents

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 6. SEM-EDX mapping. (a): Secondary electron image of EAFD region; (b): The distribution of Fe; (c): Zn; (d): O; (e): Ca; (f): Cr; (g): Si; (h): Mg; (i): Mn (Machado et al., 2006).

Fig. 7. Composition of EAFD. (a): Predominance diagram for the ZneFeeCOeCO2 (0.667 < Fe/(Zn þ Fe) < 1) system at 1100
C. Calculated using “FactSage 7.2” (‘þ’ ¼ 1.0 atm P(total)
isobar); (b): XRD pattern of EAFD.

are ZnFe2O4, Fe3O4, ZnO, and a small amount of Pb(OH)Cl and 2011), MFe2O4 (M ¼ Fe, Zn, Ni, Mn or Cd), and the other form is
Zn5[CO3]2(OH)5. It should be noted that the minimum content of free oxide (Orhan, 2005).
the crystal phase that can be resolved by XRD is more than 1 wt%. In order to further study the phase composition of EAFD, a large
Apart from the above crystal phases, other crystal phases may not number of studies have been carried out by Machado et al. (2006).
be distinguished due to the low content of XRD peak intensity or The elemental composition of medium-zinc EAFD was about zinc of
superposition between peak types. Research shows that metal el- 9.24 wt% and iron of 48.96 wt%. The results show that Pb, Cr, Ni and
ements in EAFD basically exist in two forms. The first form is a Mg in the sample exist in the form of oxides, and there are also iron
metal conjugated with iron in a composite structure (Zhang et al., chromate (FeCr2O4) and magnesium ferrite (MgFe2O4) and other

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

crystal. Fe and Zn mainly exist in the form of metal oxides FexOy, process are accompanied by a series of reactions such as decom-
ZnO and ZneFe spinel ZnFe2O4, which is consistent with the position reaction, direct reduction reaction, indirect reduction re-
research of Orhan (2005) and Zhang et al. (2011). Researchs (Baik action, carbon gasification reaction, slagging reaction, iron
and Fray, 2000; Ma and Garbers-Craig, 2009; Sofilic et al., 2004) carburization reaction, gas phase metal oxidation reaction, and gas
show that Zn exists not only in the form of metal oxide, it also exists combustion reaction. The reduction reaction stage is basically an
in the form of zinc chloride. Ca, Mg, and Si exist in the form of endothermic reaction that needs to provide a large amount of heat
Ca(OH)2, CaF2, Mg2SiO4, and 3CaO$2SiO2. In addition, there are al- energy, while the oxidation reaction of metal Zn and Pb vapours is
kali metal chlorides such as NaCl and KCl. These alkali metal an exothermic reaction, which can occur without external heat
chlorides have high vapour pressure and often volatilized prefer- source. At the same time, gas combustion also provides part of the
entially into the products during the process of carbothermal heat source for the oxidation of Zn and Pb vapours. ZnO and
reduction at high temperature, which affects the purity of the ZnFe2O4 can be reduced by carbon at a lower temperature to form
products. The minerals (Zhang et al., 2016) composed of Ca, Al, Mg, metallic iron and zinc vapour. The initial reaction temperatures are
Si, etc. will directly affect the melting point of slag (Zhang et al., 955.88
C and 791.35
C, respectively. Studies by Lee et al. (2001)
2017). The mineralogical composition of EAFD is of great signifi- show that ZnFe2O4 will decompose between 719
C and 1050
C
cance to the study of its recovery process. Table 3 lists some iden- to produce ZnO and Fe2O3. In addition, the reduction of nickel oxide
tified mineral phases corresponding to each element in EAFD. and lead oxide is prone to occur and the initial reaction tempera-
EAFD can be disposed by physical landfill, hydrometallurgy or tures are 434.25
C and 302.1
C, respectively. However, the
pyrometallurgy. At present, only pyrometallurgical process is reduction of Mn and Cr metal oxides is relatively difficult, and the
commercialized and produces economic benefits. Physical landfill initial reaction temperatures are 1426.59
C and 1257.21
C
has the advantages of easy operation, low cost and low energy respectively. Therefore, when EAFD is treated by pyrometallurgical
consumption, but its adaptability is narrow and difficult to meet method, extremely high reduction temperature is required to
various environmental standards. The valuable metals in EAFD are obtain FeeCreNi alloy with high added value.
also discarded in the process of landfill. In the process of hydro- Studies by Prabhakaran et al. (2002) and Wang et al. (2013a)
metallurgical recycling, by-products and other residues will be show that at low temperature of the coal-based direct reduction,
generated. These by-products and residues must be retreated, the carbothermal reduction rate is low and the reduction reaction
otherwise secondary pollution will easily occur. Therefore, hydro- takes a long time to complete. A large number of studies have
metallurgical treatment of EAFD only transfers the problem, but has shown that in the initial stage of the reaction, metal oxide particles
not fundamentally solved. In addition, other studies show that zinc- and carbon particles contact each other directly, and isolated metal
iron spinel in EAFD is insoluble due to its stable nature, so it is iron points are generated at these contact points (Bandopadhyay
difficult to separate zinc metal by hydrometallurgy (Yu et al., 2011). et al., 1996; Dilmac et al., 2012; Feng et al., 2011; Guanin et al.,
Pyrometallurgical process not only has the advantages of efficient 2013). As the reaction progresses, these metal particles grow up
treatment and little harm to the environment by-products, but also and connect continuously, forming a continuous metal shell
concentrates and recovers some valuable metals. This is the main covering the periphery of the core of unreacted metal oxide par-
reasons why pyrometallurgical process is suitable for commercial ticles, which seriously restrain the diffusion of carbon into the
scale application. metal shell. Therefore, if the reduction reaction is to continue,
carbon atoms must diffuse to the internal oxide particle interface
through the metal shell, and the diffusion rate of carbon in the
3. Mechanism and process of pyrometallurgical process
product layer is the limiting link of the total reduction reaction rate
of the material at the initial stage of the reaction. In addition, the
3.1. Reaction mechanism of pyrometallurgical process
coal-based direct reduction process is accompanied by carbon
gasification reaction and indirect reduction reaction. The existence
The reaction mechanism of pyrometallurgical process of EAFD is
of CO and CO2 in carbon-containing pellets is very beneficial to the
mainly based on carbothermal reaction, reducing metal oxides and
reduction reaction and carbon gasification reaction. Research by
recovering valuable metals such as zinc and iron. Based on the
Meng et al. (2002) shows that the speed of carbon gasification re-
mineral composition of EAFD, a series of possible chemical re-
action is the limiting link of coal-based direct reduction reaction.
actions, as well as the initial temperature and enthalpy change of
Smelting reduction can greatly improve the carbon diffusion rate
these reactions are summarized in Table 4. It can be seen that the
and carbon gasification reaction rate, significantly improve the ki-
process of recovering valuable metals and zinc-rich dust by pyro-
netic conditions of molten iron carburization, realize the reduction
metallurgical process of carbon-containing pellets from EAFD is a
of metal oxides and the effective separation of slag and iron in a
very complicated process. The whole reduction and oxidation

Table 3
Element in EAFD corresponds to the identified phase.

Element Identified phase

Fe Fe2O3, ZnFe2O4, Fe3O4, MgFe2O4, FeCr2O4, MgFe2O4 (Pedrosa et al., 2013), Fe3O4 (Ma and Garbers-Craig, 2006b)
Zn ZnFe2O4, ZnO (Pedrosa et al., 2013), ZnCO3, ZnCl2 (Tsubouchi et al., 2010), Zn5[CO3]2(OH)5, metallic zinc (Al-harahsheh et al., 2019)
Cr FeCr2O4, (Pedrosa et al., 2013), Cr3O4 (Ma and Garbers-Craig, 2006b), MgCr2O4, CrO (Kozlov et al., 2015)
Al Al2O3, Al2O$SiO2; Al2O$2SiO2$2H2O (Su and Shen, 2009)
Ni NiO, NieFe alloy, NieFeeCr alloy replacing Fe in Fe3O4 spinel, metallic Ni (Al-harahsheh et al., 2019)
Pb PbO, PbSO3/PbSO4, PbO.PbSO4 (Su and Shen, 2009), PbCl2, Pb(OH)Cl (Morcali et al., 2012)
Ca Ca(OH)2, CaF2 (Ma and Garbers-Craig, 2006b), 3CaO$2SiO2 (Su and Shen, 2009), CaO
Si SiO2 (Pedrosa et al., 2013), Mg2SiO4 (Ma and Garbers-Craig, 2006b)
Mg MgFe2O4, MgO (Pedrosa et al., 2013), Mg3O4, Mg2SiO4 (Ma and Garbers-Craig, 2006b), magnesiochromite (MgCr2O4) (Kozlov et al., 2015)
Mn Mn3O4 (Pedrosa et al., 2013), MnO (Su and Shen, 2009)
Cl NaCl (Ma and Garbers-Craig, 2006b), KCl, ZnCl2 (Lutandula and Kashala, 2013)
S FeS, Ni7S6, NiS2, S (Su and Shen, 2009)

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Table 4
Main reactions involved in pyrometallurgical processing of EAFD.

Type of Reaction Reaction equation Initial temperature/
C

Decomposition of ZnFe2O4 ZnFe2O4 ¼ ZnO þ Fe2O3 e 5.551

Direct reduction reaction ZnO þ C ¼ Zn(g) þ CO(g) 955.88 370.35
ZnFe2O4 þ 4C ¼ Zn(g) þ 2Fe þ 4CO(g) 791.35 872.19
FeCr2O4 þ C ¼ Fe þ Cr2O3 þ CO(g) 1054.47 220.48
3Fe2O3 þ C ¼ 2Fe3O4 þ CO(g) 319.78 132.03
Fe3O4 þ C ¼ 3FeO þ CO(g) 696.39 209.38
FeO þ C ¼ Fe þ CO(g) 726.41 155.31
PbO þ C ¼ Pb(l) þ CO(g) 302.10 113.16
CuO þ C ¼ Cu(l) þ CO(g) 15.18 57.39
MnO þ C ¼ Mn þ CO(g) 1426.59 274.40
Cr2O3 þ 3C ¼ Cr þ 3CO(g) 1257.21 246.65
NiO þ C ¼ Ni þ CO(g) 434.25 128.97
CdO þ C ¼ Cd(g) þ CO(g) 598.94 260.26
Gasification reaction C þ CO2(g) ¼ 2CO(g) 706.16 172.47
Indirect reduction reaction ZnO þ CO(g) ¼ Zn(g) þ CO2(g) 1317.90 197.89
ZnFe2O4 þ 4CO(g) ¼ Zn(g) þ 2Fe þ 4CO2(g) 1330.96 182.31
3Fe2O3 þ CO(g) ¼ 2Fe3O4 þ CO2(g) e 40.40
Fe3O4 þ CO(g) ¼ 3FeO þ CO2(g) 637.10 36.91
FeO þ CO(g) ¼ Fe þ CO2(g) Inverse 570.96 17.16
PbO þ CO(g) ¼ Pb(l) þ CO2(g) e 59.31
CuO þ CO(g) ¼ Cu(l) þ CO2(g) e 115.08
Cr2O3 þ 3CO(g) ¼ Cr þ 3CO2(g) e 270.76
CdO þ CO(g) ¼ Cd(g) þ CO2(g) 434.80 87.79
Slag reaction Al2O3 þ 2SiO2 ¼ Al2O3$2SiO2 e 156.194
3Al2O3 þ 2SiO2 ¼ 3Al2O3$2SiO2 e 29.58
Al2O3 þ FeO ¼ FeAl2O4 e 52.334
CaO þ SiO2 ¼ CaSiO3 e 89.16
2CaO þ SiO2 ¼ 2CaO$SiO2 e 134.59
2CaO þ Al2O3 þ SiO2 ¼ CaO$Al2O3$2SiO2 e 95.58
Carburization reaction 3Fe þ 2CO(g) ¼ Fe3C þ CO2(g) e 147.23
3Fe þ C ¼ Fe3C 795 25.10
Oxidation reaction 2Zn(g) þ O2(g) ¼ 2ZnO e 961.80
2 Pb(g) þ O2(g) ¼ 2PbO e 826.55

very short time. However, when the reduction melting temperature 900
C, the interfacial chemical reaction of carbothermal reduction
is high, the liquid lead will volatilize and lead oxide content in zinc- changes from solid-solid reaction to gas-solid reaction. Because, as
rich dust will increase sharply. the reaction progresses, the reduction product metal layer and slag
Similar to the reduction reaction of iron ore pellets, the phase layer gradually fill the gap between dust particles and carbon
unreacted core model is also applicable to carbothermal reduction particles. As a result, the contact area between reducing agent and
of EAFD pellets. The reaction occurring at the active reaction metal oxide is reduced, and the solid-solid reaction is difficult to
interface is shown in Fig. 8. At the initial stage of the reaction, the continue. However, CO and CO2 can diffuse into and pass through
solid reactant particles have sufficient contact, and the solid-solid the porous product layer and continue to react with metal oxides in
direct reduction reaction can proceed smoothly. The study by the pellets. At this time, compared with the rate of gas-solid
Zheng et al. (2021) shows that when the temperature rises above reduction reaction, the role of solid-solid reduction reaction is

Fig. 8. Reaction of Zinc-containing EAFD reduced by carbon.

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

negligible (Mackenzie and Shuttleworth, 2002; Pandey and method and Coke-packed bed method. It can be seen that all kinds
Sharma, 2000; Sharma, 2007). The reaction system changed from of pyrometallurgical processes have their own advantages and
solid-solid direct reduction reaction to gas-solid indirect reduction disadvantages. The advantages of direct reduction method in
reaction at the initial stage of the reaction, and Boudouard reaction treating EAFD lie in lower operation cost, relatively simple process
(Carbon gasification reaction) (Bost et al., 2016) became the control and less environmental pollution. The disadvantages are often
link of the reaction. Hong et al. (2003) established the kinetic model manifested in low product quality and the equipment is easy to be
and studied the carbothermal reduction process of ZnO through breakdown. The advantages of smelting reduction method lie in
non isothermal experiments. The activation energy of carbon high process temperature, complete reaction and higher removal
reduction of ZnO is calculated to be 222 kJ mol1, and the activation rate of various valuable metals, but the heat consumption is also
energy of Boudouard reaction is between 200 kJ mol1 and larger and the waste heat is difficult to be recycled.
250 kJ mol1. The results also show that if the gaseous products are
not removed from the system in time during carbon reduction of 3.2.1. Rotary kiln process
ZnO, the indirect reduction reaction will dominate with the in- Rotary kiln process is a general term for direct reduction of
crease of CO and CO2 partial pressures, and the reduction reaction metallurgical solid waste with a rotary kiln as the core equipment.
rate will be controlled by the Boudouard reaction. At this time, the After decades of development, in addition to the classic Waelz kiln
reaction rate of heterogeneous reaction mainly depends on the process, Japan’s Kawasaki process, SDR process, SL/RN process, etc.
diffusion rate of reaction components and the interfacial chemical are also derived. The characteristics and application status of each
reaction rate (Cheng et al., 2016). The general steps of the process process (Anon, 1989; Strohmeier and Bonestell, 1996) are shown in
include the external diffusion of the gas reactant and the products Table 6. It can be seen that the main products of recovering EAFD by
in the solid surface boundary layer, the internal diffusion of the gas rotary kiln method are zinc oxide and direct reduced iron, and the
reactant and the products through the solid product layer, and the removal rate of zinc can reach more than 94%. According to the
interfacial chemical reaction between the gas and the solid reac- different production scale of the plant, the annual dust treatment
tant. In the products of carbothermal reduction of EAFD, the amount of rotary kiln process varies from 100 to 350 thousand tons/
evaporation rate of metal elemental substance is mainly affected by a.
interfacial chemical reaction, vapour diffusion and temperature. At present, the mainstream EAFD treatment process is still
The boiling point of Zn is 907
C, and the equilibrium vapour Waelz kiln process, and about 83% of the EAFD in the world is
pressure of Zn is 93.2 kPa at 900
C, which is about equal to a large recycled through Waelz kiln method (Yakornov et al., 2017).
standard pressure. The evaporation rate of Zn(g) is slower when the Metallic zinc recovered by Waelz kiln process accounts for about
temperature is lower than 900
C. With the change of carbothermal 5.2% of the world’s refined zinc production (International Lead and
reduction mechanism, the temperature increases, and the interfa- Zinc Study Group, 2020). Waelz kiln body is generally 50 m long
cial chemical reaction and diffusion of CO and Zn (g) are improved. and slightly inclined, with a diameter of 3e4 m and rotating speed
In the temperature range of 900
Ce1100
C, the evaporation rate of of 0.5e1.6 rpm. The residence time of materials in Waelz kiln is
zinc will increase rapidly (Xing et al., 2005). The boiling point of determined by bricklaying, kiln length and rotation speed, usually
lead metal is 1751
C, and the equilibrium vapour pressure of Pb is between 4 and 6 h (Mager et al., 2000). Suetens et al. (2014b), and
only 42.24 Pa at 900
C. Pb does not volatilize in the whole car- Ruetten et al. (2011) took the high-zince EAFD (zinc containing
bothermal reduction process, and may volatilizes in the form of 23 wt%) as the research object, set the zinc removal rate of Waelz
PbCl2, which boiling point is 951
C. PbCl2 is also the main lead- kiln process to reach 90%, finally obtained that the energy con-
containing compound in EAFD. sumption of Waelz kiln process to recover EAFD is 2.1 GJ$ton1. The
After carbon thermal reduction of EAFD, the collected metal flow and parameters of various rotary kiln process are similar.
vapours such as Zn, Pb volatilizes into the flue gas recovery system Taking Waelz kiln process as an example, the basic process flow is
for further oxidation and enrichment, Fe, Cr, Mn and a small shown in Fig. 9. Firstly, EAFD, pulverized coal, and binder are mixed
amount of metal Ni will be retained in the solid products after with water and then pelleted. Moist materials are sent into the kiln,
reduction. The direct reduced iron obtained from the reduction of dried and preheated by countercurrent kiln gas. After entering the
EAFD can be directly used as raw material for ferroalloy smelting, or reduction zone, the temperature reaches 1100e1200
C, and the
after simple treatment, it can be used as secondary raw material for metal oxide starts to be reduced. High vapour pressure zinc, alkali
steel production (Lin et al., 2017). Among them, metals such as Cr, metals, and their compounds are selectively volatilized from the
Mn, and Ni etc., which contain more contents in low-zinc EAFD, mixture. Then the air at the end of the kiln is controlled to inject,
also increase the added value of steel products. and the high vapour pressure metal oxide in the gas phase is taken
away from the kiln, while a small amount of metal iron in the
3.2. General situation of pyrometallurgical process burden will be oxidized again, and then a by-product called Waelz
slag will be formed (Coronado et al., 2016). Finally, the slag is dis-
The existing EAFD pyrometallurgical process are mainly divided charged through a wet deslagging system, and the unreacted coke
into two categories: direct reduction method and smelting reduc- is separated from the slag by magnetic separation and reused. Dust-
tion method. Both processes reduce zinc, lead and other metal containing waste gas is treated in three stages in the downstream
oxides in dust into metal vapours to separate it from residue. The system. In the first stage, coarse particles formed by collision and
difference is lies in that the direct reduction method does not melt extrusion between materials do not react and are mechanically
metal oxides at low temperature, iron oxides are partially reduced entrained out of the rotary kiln by excessive airflow. This part of
to direct reduced iron, while the smelting reduction method melts particles will be isolated in the dust chamber and returned to the
and reduces almost all metal oxides in dust. The common pyro- kiln with new materials. In the second stage, the dusty waste gas is
metallurgical processes include rotary kiln method, rotary hearth cooled, Waelz oxide in the dusty waste gas is separated in a pre-
furnace method, Primus method (Nakayama, 2012), ESRF method, cipitator and sent to a zinc refinery. The dust-free waste gas in the
and Coke-packed bed method (Itaya et al., 1990). And their char- third stage is purified to remove mercury, cadmium and dioxin,
acteristics are shown in Table 5. Among them, the direct reduction finally discharged into the atmosphere through a fan
methods include rotary kiln method, rotary hearth furnace method (Antrekowitsch et al., 2014).
and Primus method. The smelting reduction methods include ESRF It is worth noting that the rotary kiln of Waelz process can be
10
 Table 5

J. Wang, Y. Zhang, K. Cui et al.

Comparison of various pyrometallurgical processes for EAFD.

Process Products Plants Advantages Disadvantages

Rotary Kiln Waelz Oxide, Zinc-rich dust, Germany Baden Steel, Japan (1) Simple process and Less (1) Low productivity.
DRI Mizushima Company operation steps. (2) Low ZnO content of Zinc-
(2) Reliable process and well- rich dust produced.
established technology. (3) High maintenance costs.
(4) High residue. (about 700
e800 kg/t raw material dust)
(Antrekowitsch et al., 2015).
(5) Only economical for
medium and high-zinc wastes.
(zinc content >16 wt%) (Leclerc
et al., 2002).
RHF Zinc-rich dust, Japan JFE Steel Corporation, (1) Proven technology, (1) High initial investment and
DRI China Rizhao Steel industrial plant operating. operational costs.
(2) Simple process flow. (2) High energy costs.
(3) High value pig iron product. (3) Strict operation
(4) High metallization. temperature requirements.
(Mishra et al., 2002).
(4) Easily blocked flue gas
system.
PRIMUS Zinc-rich dust, Paul Wurth Luxembourg (1) Low reaction temperature (1) The furnace is easy to
DRI (1000e1100
C), low energy corrosion due to the
cost. (Roth et al., 2001). volatilization of alkaline
(2) No pelletization required of compounds.
raw material. (2) Limited productivity, due to
(3) Flexible process, can be used the multi-stage hearth size.
for comprehensive treatment of
11

dust, slag and scrap.

(Hansmann et al., 2000).
(4) Variable volume and
number of layers, which can
adapt to the material.
ESRF Pig iron, Zinc- Taiwan KATEC R&D Company, (1) Clean energy and complete (1) High energy costs.
rich dust Japan Steel Plantech reaction. (2) The waste heat energy is
(2) Produce hot metal, which difficult to recycle.
add to the furnace without
ingot casting.
(3) High temperature (more
than 1250
C), complete
decomposition of dioxin.
(4) Slag with low heavy metal
content can be widely used.

Journal of Cleaner Production 298 (2021) 126788

Coke-packed Zinc-rich dust, Japan Kawasaki Steel (1) Complete metallization and (1) Extreme heat consumption.
bed Molten iron, Corporation slag separation. (2) The waste heat energy is
Slag (2) No pelletization required of difficult to recycle.
raw material. (3) Zinc adhesion is easy to
(3) Recovery of both zinc and appear on furnace top wall.
lead provides high value (4) Very high temperature
products. requires expensive refractories.
(4) No secondary waste
discharges.
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Table 6
The characteristic and application of rotary kiln process.

Process Production Plants Dezincification rate Capacity

Waelz kiln process 55 - 60 wt% ZnO, 51e58% DRI Germany Baden steel More than 90% 100 Kt/a
SL/RN process Zinc-rich dust, DRI Japan Fukuyama plant More than 86% 350 Kt/a
Kawasaki process 90% DRI, Zinc-rich dust Japan Mizushima plant More than 94% 180 Kt/a
SDR process 92%e95% DRI, Zinc-rich dust Japan Sumitomo Corp More than 90% 156 Kt/a

Fig. 9. Simplified flow diagram of a Waelz plant.

Fig. 10. Main reactions in the reduction stage within the Waelz kiln.

Table 7
Chemical analysis (wt.%) of the inputs and products of the Waelz kiln process.

Element compound EAFD (wt.%) Ferrous product (wt.%) Waelz Oxide (wt.%)

Zn 18.0e25.0 0.2e2.0 55.0e58.0

Pb 2.0e7.0 0.5e1.0 7.0e10.0
Cd 0.03e0.1 <0.01 0.1e0.2
F 0.2e0.5 0.1e0.2 0.4e0.7
Cl 1.0e4.0 0.03e0.05 4.0e8.0
C 1.0e5.0 3.0e8.0 0.5e1.0
FeO 20.0e38.0 30.0e50.0 4.0e7.0
Femet/Fe e 80.0e90.0 e
CaO 6.0e9.0 15.0e25.0 0.7e1.2
SiO2 3.0e5.0 6.0e12.0 0.5e1.0
Na2O 1.5e2.0 1.2e1.6 0.1e0.2
K2O 1.0e1.5 0.7e0.9 0.1e0.2

12
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

divided into a bottom material reduction area and an upper powder, replace powder with pellets, and improve the metallur-
countercurrent gas oxidation area. The gas-solid, solid-solid and gical properties of pellets, especially the falling strength and
gas-gas reactions in the kiln are mainly carried out in these two compressive strength of pellets, so as to inhibit the pulverization of
areas. Fig. 10 shows the main reactions occurring in these two areas the material and achieve the purpose of reducing the ring forma-
on the cross section of the rotary kiln. It can be seen that the tion (Vyatkin et al., 2015).
metallic oxides are reduced by carbon and CO at the bottom of the
furnace, high vapour pressure metals are volatilized (such as Zn),
3.2.2. Rotary hearth furnace (RHF) process
and are partially oxidized in the upper oxidation area to obtain
Rotary hearth furnace (RHF) is another important new coal-
metal oxides and CO2 that enter the oxidation chamber with kiln
based direct reduction metallurgy process developed in recent 30
gas for further oxidation. At the same time, the heat released in the
years. It has been put into use globally. Due to its advantages of
oxidation reaction process can effectively act on the furnace
wide adaptability of raw materials, low energy consumption and
burden. Iron remains in the bottom burden waiting for the next
less environmental pollution, it has been used to treat metallurgical
separation and recovery.
solid wastes such as electric furnace dust (EAFD), blast furnaces
Waelz process can effectively recover iron, zinc and other metal
dust/slug (BFD, BFS), basic oxygen furnace dust (BOFD), basic oxy-
elements in EAFD and enrich lead to a certain extent. Table 7 shows
gen steelmaking slug (BOSS), etc. At present, FASTMET, ITmk3, Hi-
the composition change of materials before and after typical Waelz
QIP, COMET and other processes have been developed by rotary
process treatment (Buse et al., 2014; Mager et al., 2003). It can be
hearth furnace process (Tsutsumi et al., 2010). Table 8 shows the
seen that the zinc content of medium and high-zinc EAFD before
element composition of various iron products obtained by recov-
recovery is 18e25 wt%, and the zinc content in zinc-rich dust
ering metallurgical solid waste from these four types of rotary
products is 55e58 wt%. The content of lead in zinc-rich dust rea-
hearth furnace processes. It can be seen that the recovered products
ches 7e10 wt% after enrichment from the original 2 to 7 wt%. Non-
of the rotary hearth furnace processes are mainly composed of
metallic elements such as F and Cl are easily enriched into zinc-rich
direct reduced iron (DRI) and pig iron. The content of iron in the
dust. The metallization rate of iron products can generally reach 80
products is above 70 wt% and the highest can reach 95.8 wt%, while
to 90 wt%, and there are still many oxides in iron products, such as
the content of zinc is generally not more than 0.004 wt%, almost no
CaO content reaching 15 to 25 wt%, SiO2 content reaching 6 to 12 wt
lead can be detected. The content of nonmetallic elements is rela-
%.
tively low, such as P (0.04e0.06 wt%), S (0.015e0.35 wt%), C
Up to now, rotary kiln process is still considered as a mature and
(0.2e4.3 wt%), and also contains a certain amount of SiO2. High
effective process method for treating EAFD. It has the advantages of
quality ferrous product can be obtained by recovering metallurgical
simple process, no liquid slag and less environmental pollution.
solid waste in rotary hearth furnace.
However, this process also has many drawbacks, among which the
The classic model diagram of the rotary hearth furnace plant
problem of ring formation occurs frequently and is difficult to
and the rotary hearth furnace with 200 Kt annual capacity of Rizhao
avoid. The solid furnace burden will slip down as the rotary kiln
Steel in China are shown in Fig. 11 (a) and (b), respectively. Fig. 12
rotates. It leads to five kinds of motion modes: sliding, collapsing,
shows a process flow chart of the typical rotary hearth furnace
rolling, waterfall falling and centrifugal rotation. Under normal
process. It can be seen that the complete rotary hearth furnace
circumstances, the rotary kiln is in the state of collapse, tumbling
process basically includes a feeding device, a distributor, a rotary
and waterfall falling, which are mixed or one goes against the other.
hearth furnace, a gas transmission pipe network, a product trans-
It is also these states that lead to the extrusion, impact, pulveriza-
portation device, a flue gas recovery and dust removal device, etc.
tion and ring formation in the kiln. Because of the complex
In the process, the EAFD and pulverized coal are weighed propor-
composition of EAFD, the melting of the low melting point metal
tionally, and binder is added to the mixture and sent to the mixer
will increase the adhesion of the burden, and the low melting point
for uniform mixing. After mixing evenly, it is pressed into carbon-
of slag or the use of pulverized coal with low ash melting point will
containing pellets by a counter-roller ball press. After screening,
increase the liquid phase, erode the lining and at the same time
and evenly the pellets are sent to the distributor by belt conveyor,
make the burden sticky, forming rings after repeated rolling. During
distributed to the rotary hearth furnace for drying and reduction.
the operation of rotary kiln, if the local temperature is too high, it
The pellets remain relatively stationary with the furnace bottom
will also cause the burden to ring. In the daily production, corre-
and move circumferentially at a certain rate, which reducing pellet
sponding measures are adopted to deal with the problem of ring
pulverization caused by mechanical collision. The exhaust fan ex-
formation. For example, pulverized coal with high ash melting
tracts the hot gas in the opposite direction to the rotation direction
point, low ash and gangue content is used as reducing agent.
of the furnace bottom, thus realizing countercurrent heat exchange
Strictly control the temperature distribution in the kiln to ensure
to increase the thermal efficiency. In fact, most of the heat gener-
that the reduction temperature is lower than 1300
C to reduce the
ated by the two groups of blowing nozzles above the furnace will
amount of liquid phase in the material, reduce the proportion of
quickly pass through the materials. Therefore, although radiation

Table 8
Chemical composition of products from various rotary hearth furnace.

Process Input waste Products Chemical composition(wt.%) Reference

Fe Zn Pb P S C SiO2

FASTMET BFD DRI 70.5 0.004 e e 0.35 1.13 e Muwanguzi et al. (2012)
BFS
BOSS
ITmk3 BFD Pig iron Bal. e e 0.06 0.015 2.5e4.3 0.2 Wang et al. (2013b)
BOFD
Hi-QIP BFD Iron pebbles Bal. <0.01 <0.01 0.04 0.25 2.1e3.0 0.08 Sawa et al. (2001)
BOFD
COMET Iron ore mixture DRI 88.1e95.8 e e e 0.032 0.2 1.86 e et al. (1999)
Borle

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 11. Rotary hearth furnace plant. (a): Classic model diagram; (b): Capacity of 200 Kt/a RHF of Rizhao Steel in China.

Fig. 12. Process flow chart of RHF.

Fig. 13. Schematic diagram of heat transfer and reaction process in RHF.

gives a lot of heat, the total heat transfer efficiency is low. out, before it is transferred to the pellets completely, due to the
Fig. 13 shows the heat transfer and reaction process in the rotary negative pressure environment in the furnace. In addition to the
hearth furnace, the pellets gradually enter the high temperature solid-solid reaction with carbon, some metal oxides also undergo
reaction zone of 1250
Ce1350
C along with the furnace bottom. gas-solid reaction with CO during the reduction process. CO diffuses
The heat transferred to the pellets comes from the radiation from outside to inside, which conforms to the “unreacted core”
emitted by the gas above the pellets and at the bottom of the model. Considering the reaction and heat transfer, the particle size
furnace. The heat is mainly generated by the radiation, but not of the pellets should be controlled within 20 mm. The reduced
conduction. Most of the heat generated by the gas will be carried metal zinc, lead and some alkali metals directly volatilize into the

14
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Table 9
The characteristic and application of rotary RHF in China and abroad (Kurunov, 2012; Zhang et al., 2015).

Plants Outside Diameter (m) Width (m) Capacity (10 Kt/a) Products Time to market

U.S.A Dynamics 50.0 7.0 52 DRI (Metallization rate is 85%) 1998

Japan Nippon Steel Guangtan 21.5 2.8 14 DRI (Metallization rate is 90%) 2000
Zinc-rich dust (Zn content 47.70 wt%)
Japan Nippon Steel Junjin 20.4 4.0 13 DRI (Metallization rate is 75e85%) 2000
Zinc-rich dust (Zn content 63.4 wt%)
Japan Kobe Kakogawa Steel 8.5 1.25 1.1 DRI (Metallization rate is 85%) 2001
Zinc-rich dust (Zn content 63.4 wt%)
China Anhui MaSteel 20.5 4.9 20.0 DRI (Metallization rate is 80%) 2009
Zinc-rich dust
China ShanDong Rizhao Steel 21 5 2*20 DRI (Metallization rate 80%) 2010
China ShanDong Laiwu Steel 21 5 20.0 DRI (Metallization rate >70%) 2010
China ShanDong ShaSteel e e 30 DRI (Metallization rate >80%) 2011
Zinc-rich dust

furnace gas due to high vapour pressure, and reoxidize under the CO2 within 15e20 min then form a layer of iron oxide in DRI shell
oxidizing atmosphere of the furnace gas. This part of metal oxides (Kuwauchi and Barati, 2013). These shortcomings make rotary
passes through the waste heat recovery system and the waste gas hearth furnace technology more suitable for treating metallurgical
treatment system in turn along with the furnace gas and are finally solid waste such as EAFD to recovering valuable metals. Table 9
collected in the form of metal oxide dust. The study by Ibaraki and shows the characteristics and application status of various types
Oda (2002) shows that the total heat consumption from carbon and of rotary hearth furnace processes worldwide from 1998 to 2011. It
gas is about 5.9e6.4 GJ$ton1, the energy consumption from gas is can be seen that the products recovered from EAFD by rotary hearth
about 2.3 GJ$ton1, and the heat recovery from waste heat pot is furnace are mainly direct reduced iron and zinc-rich dust, the zinc
about 0.9 GJ$ton1. The average energy consumption of rotary content in the products is 47.70 wt% to 63.40 wt%, and the metal-
hearth furnace is about 6.1 GJ$ton1, which varies with operating lization rate of direct reduced iron products is 75%e96%, and the
conditions and burden composition. This data is higher than the treatment capacity of each process varies from 10 Kt/a to 520 Kt/a.
results of Suetens et al. (2014b) they calculated the energy con- The results of Nakayama and Taniishi (2011) show that the rotary
sumption of 4.0 GJ$ton1 based on the data of the first commercial hearth furnace process may be superior to Waelz kiln technology in
RHF recovery electric furnace by-product plant in Britain in 2012. commercial and environmental aspects. Under the conditions of
The powder obtained from the product screened will be carbon-oxygen ratio 1.0, operating temperature 1230
C and reac-
returned to the ball-pressing again, and the metallized pellets will tion time 15 min, the iron metallization degree, Zn removal rate and
be cooled and then sent to storage in product bin in a nitrogen-rich alkali metal (K, Na) removal rate of reduced EAFD pellets can reach
atmosphere, or directly transported to the steel-making plant. In 75%, 95%, and 80%, respectively.
order to prevent the metal from oxidizing again in the production The rotary hearth furnace process has great treatment capacity
process, a certain reducing atmosphere is often ensured by con- per unit area, and the existing reports show that the maximum
trolling a low air/gas ratio (Zhang et al., 2013). However, in the daily annual treatment capacity of EAFD recovered by the rotary hearth
production process, gas in the furnace is mainly CO2 with slight furnace process can reach 300,000 tons per year. At the same time,
oxidation property. DRI reduced from iron oxide will be oxidized by the rotary hearth furnace process is also a mechanically simple and

Fig. 14. Primus process for treatment of EAFD.

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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

reliable process, which is easier to operate than Wealz kiln. How-

ever, the disadvantage of this process is that the requirements for
raw materials are strict. The rotary hearth furnace process is more
suitable for recycling EAFD with low-zinc content (<5 wt%), which
is easy to cause zinc oxide blockage at high-zinc content. In addi-
tion, if the compressive strength of raw materials is not enough, a
lot of broken pellets and fine particles will return to the granulation
step, thus reducing the process productivity (Suetens et al., 2014a).
After a long period of development, these defects have been
improved to some extent, but due to the large initial investment in
equipment, the economic benefits of the process must be further
improved.

3.2.3. PRIMUS process

Different from the rotary hearth furnace process, Primus process
is suitable for treating metallurgical solid waste with zinc con-
taining more than 5 wt% and recovering valuable metals, such as
BFD, BFS, BOFD, EAFD and sludge or dust generated by small rolling
mills. Recycling EAFD, the quality of pig iron produced by Primus is
similar to that produced by blast furnace, and zinc-rich dust (more
than 55 wt% zinc oxide), and inert slag that can be used for road
construction are generated at the same time. The main feature of
this process is to use multi-hearth technology. Primus’s reaction
furnace consists of cylindrical chambers with multiple stacked Fig. 15. Concept of ESRF. (a): Flow chart of the process; (b): Reactions in EAF; (c): On-
annular compartments to form a multi-stage furnace. The floor of site photos of tapping port and slag outlet.
the furnace is made of refractory bricks, and a rake handle driven by
a rotating cooling column is located next to the upper side of the
various hearths, as shown in Fig. 14 (a). The mixture of coal and temperature (1000e1100
C), direct mixing does not need granu-
EAFD enters the first layer furnace from the top of the furnace. With lation, and the production cost is low; Secondly, Primus process is
the help of the scraper on the rake handle, the material is trans- very flexible, which can be used for comprehensive treatment of
ported from one furnace to the next, and from the center to the dust, slug and debris. The furnace volume and the amount of
wall. The whole furnace can be divided into drying zone, heating furnace layers are variable, which can adapt to the requirements of
zone and reduction zone from top to bottom. The materials are the various materials; Thirdly, the quality of the products recovered
firstly dried in the drying zone and then sent to the lower part by by Primus process is high, the metallization rate of DRI is more than
scraper. In the heating zone, impurities such as binding water, oil 90% (Roth et al., 2001), the removal rate of Zn is about 90%e96%
and so on are removed. Finally, the material enters the bottom (Hansmann et al., 2000). However, the disadvantage of this process
reduction zone where metal oxides are reduced. Fig. 14 (b) shows is that the evaporation of alkaline compounds during rapid stirring
the main reactions in the typical reduction zone, where ZnO is and reduction easily leads to furnace corrosion. In addition, the size
reduced to zinc vapour, and iron oxide is reduced to metallic iron. of the multi-stage hearth is limited in order to maintain good dy-
The secondary combustion of CO formed in the reduction process is namic conditions for the feed, which limits its productivity
made by blowing air at the nozzle between the two furnaces, which (Kolbeinsen, 2010).
can raise the furnace temperature up to 1100
C. The dust mixture The direct reduction process for treating EAFD, represented by
of carbon with EAFD is fully heated in the process of descending rotary kiln, rotary hearth furnace and Primus process, has been
from the upper furnace. When it reaches the lower furnace, there widely used and developed very maturely. However, compared
are basically reducing atmosphere around the carbon containing with smelting reduction process, the direct reduction process has
materials. This layer of reducing atmosphere forms a boundary the disadvantages of low average recovery rate and large residual
layer with the oxidation atmosphere between the two floors. At this toxic heavy metals in recovering valuable metals from EAFD. The
time, the reduction of metal oxide should be further carried out. smelting reduction process can melt and reduce almost all metal
The high vapour pressure metal and some volatile compounds rise oxides in EAFD. The existing smelting reduction processes for
with the furnace gas, and are discharged into the gas purification recovering EAFD include ESRF process, Coke-packed bed, EMPF by
system through the waste gas outlet. The basic compounds ELKEM, PIZO by Heritage Technology, Ausmelt process, Tetronics
vaporized are collected in the bag filter. After reaction in oxidation plasma furnace and others.
chamber, zinc and lead vapours are recovered in the form of zinc
oxide and lead oxide. The removal rate of zinc can reach 95%. At the 3.2.4. Electric smelting reduction furnace (ESRF) process
same time, the iron oxide is reduced to direct reduced iron at the ESRF process abbreviated from electric smelting reduction
bottom of the furnace with a metallization degree of 90e95%, furnace, is a new smelting reduction process developed by Taiwan
which is used for blast furnace smelting or electric furnace steel- KATEC R&D Company and Japan JP Steel Plantech Company to
making after cooling. recover valuable metals from metallurgical solid waste. This pro-
Several hundred tons of EAFD and part of steel rolling sludge cess was first put into trial operation in Taiwan in December 2009,
were treated by Primus process in the pilot stage. The results followed by commercial operation and gradual commercialization
showed that the zinc removal rate was 96%, the lead removal rate in September 2010. The ESRF process is characterized by using only
was more than 90%, the chlorine removal rate was more than 90%, electrical energy to produce extremely high temperatures. The
and the iron metallization rate was more than 98%. These data EAFD is completely melted under high temperatures. Its core
show the excellent performance of the process. The advantages of equipment is an electric arc furnace that does not need fossil fuels
Primus process are as follows. Firstly, it has relatively low process to provide heat energy. The gas after the reduction is basically free
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J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

of nitride sulfide waste gas and secondary dust particles formed metals in the slag and no harmful substances remain. The slowly
after coal combustion. At the same time, ESRF process provides a cooled slag produces crystalline structure and can be used for
variety of recovery schemes for reduced high vapour pressure various purposes. The disadvantages of ESRF process are that
metals such as zinc and lead and alkali metal chloride (Jouhara compared with using fossil fuels for energy supply, electric heating
et al., 2018). Fig. 15 (a) shows the main flow chart of ESRF process has high energy cost, low heat energy utilization rate of waste gas,
for treating EAFD. Firstly, the mixture of sintered EAFD, coke and and only a part of energy is used to preheat the raw materials
limestone are granulated, and then sent into the electric arc furnace entering the furnace. Generally speaking, ESRF method is a prom-
through a feeder for smelting reduction reaction. Air is blown above ising process for smelting reduction to recover EAFD.
the material, and the airflow brings carbon monoxide and zinc
vapour into the combustion chamber. The oxidation atmosphere of 3.2.5. Coke-packed bed process
the combustion chamber is controlled by introducing secondary air Coke-packed bed process is a smelting reduction process for
to ensure that the metal zinc in the gas phase is fully oxidized. The metallurgical solid waste. It is developed by Kawasaki Steel Corp in
powder of large particles of iron oxide and carbon deposited at the Japan (Itaya et al., 1990). The process was first used to recover
bottom of the combustion chamber is recycled to ESRF. A large converter dust containing chromium and nickel and was industri-
number of crude zinc oxide and chloride particles are discharged alized in 1994. Then, a pilot test of EAFD recovery was carried out in
from the combustion chamber along with hot waste gas, and are 1996, which determined the technical parameters and verified the
rapidly cooled by a multi-tube gas cooler. By accurately controlling feasibility of the process. The process uses a shaft furnace with a
the temperature of the gas cooler, the chloride on the surface of the packed bed of coke. The function of coke is similar to that of the
vertical tube is solidified, thus removing the chloride. Finally, zinc carbon skeleton in blast furnace ironmaking. It supports the burden
oxide is recovered by bag filter, and the removal rate of zinc oxide and is also as a fuel and reducing agent. Two tuyeres are arranged at
can reach 65%e82%. Fig. 15 (b) shows a series of chemical reactions the middle and lower part of the furnace (Fig. 16), and oxygen-
between materials and reducing agents in the electric arc furnace at enriched hot air is blown through the two tuyeres. Due to the
high temperature. Metals such as Zn are reduced and then removed efficient heat exchange between the rising gas and the falling coke
from one side of the waste gas port along with furnace gas. Metal in the furnace, a high-temperature centralized reduction area is
iron is reduced and melted then layered with slag at high tem- formed between the upper and lower tuyeres. In order to
perature. The on-site photos of tapping port and slag outlet are completely reduce metal oxides, the temperature providing most of
shown in Fig. 15 (c). The collected high carbon pig iron with a the heat to the lower tuyere is raised to above 1550
C. Fine powder
carbon content of 3.44 wt% will be returned to the EAF steel plant, materials (such as EAFD and coke) are injected through the upper
the slag containing 0.44 wt% zinc and 0.03 wt% lead will be slowly tuyere, then melted and reduced instantly in the gyrator inside the
cooled in the slag tank to form a crystalline structure. The content shaft furnace. After that, molten metals such as iron, chromium,
of Pb, Cd and other heavy metals in this slag is very low, which nickel and molten slag drip into the furnace. High vapour pressure
makes it not only suitable for direct landfill, but also can be used as such as zinc are extracted at the top of the furnace, and zinc vapour
building aggregate (Nakayama, 2012). carried with waste gas is collected by water spray quenching in
The electrode of ESRF process uses extremely high temperature quenching equipment and Venturi scrubber, and then recovered as
to melt all substances in solid waste, making it possible to recover slurry (Hara et al., 2000). ISHIWATA et al. (2001) treated EAFD with
iron in the form of metallic iron, thus realizing extremely high zinc of 27.7 wt%, iron of 25.0 wt%, and lead of 3.22 wt%, the results
separation rate of heavy metals from slag. Compared with the use showed that zinc and lead were successfully recovered into zinc-
of fossil fuels, electric heating does not generate waste gas, the rich dust (60 wt% zinc and 6.2 wt% lead), their contents in metal
complete melting state also reduces the existence of impurity iron (0.005 wt% zinc and 0.001 wt% lead) and slag (0.01 wt% zinc
particles in the airflow, the reaction is more complete, and the and 0.001 wt% lead) were very low, and the toxic equivalent con-
recovered ZnO has higher purity content. At the same time, most of centration of dioxin in waste gas was 0.0001 ng g1, indicating that
the iron in the dust is recovered in the form of molten pig iron, dioxin decomposed in smelting reduction furnace was not syn-
which can be directly added to the electric arc furnace without thesized again to meet environmental requirements.
using a casting machine to make ingots. Finally, there is little heavy High added value molten metal, zinc-rich dust and high tem-
perature slag can be obtained by coke-packed bed process.
Compared with other processes, it has the advantages of high slag-
iron separation efficiency; Direct use of EAFD, pulverized coal or
coke powder and other raw materials and fuels without lumping
and granulation; Almost all zinc and lead are recovered; No sec-
ondary waste is discharged. However, its disadvantage is that the
smelting reduction process consumes a large amount of heat, and a
large amount of sensible heat of furnace gas cannot be effectively
recovered or utilized. In addition, zinc adhesion is easy to occur on
the top wall surface of the furnace, so it is difficult to control the
oxidation of the furnace gas by maintaining the top gas tempera-
ture and the ratio of CO2/CO in the area where zinc vapour is stable
(Itaya et al., 2017).

4. Characterization of EAFD products treated by

pyrometallurgy

After the EAFD is recovered by pyrometallurgical process, zinc

and lead are reduced and volatilized in the gas phase to obtain dust
products containing a small amount of lead compounds and a large
Fig. 16. Coke-packed bed process for treatment of EAFD. amount of zinc oxide, and zinc dust is also obtained by directly
17
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 17. SEM images of EAFD pellets. (a): raw pellet reduced with charcoal; (b), (c), (d): reduced with charcoal at 800
C, 1050
C, 1150
C respectively; (e): raw pellet with petroleum
coke; (f), (g), (h): reduced with petroleum coke at 800
C, 1050
C, 1150
C respectively (Buitrago et al., 2018).

condensing zinc vapour, collectively referred to as zinc-rich dust. metal lead phase disappears, which may be related to the melting
Zinc-rich dust will be sent to the refinery to separate zinc and lead point of lead oxide (888
C). Energy Dispersive Spectrometer (EDS)
to produce zinc ingots, lead ingots or high-purity zinc oxide pow- analysis showed that the iron content began to increase gradually
der. The recovered molten metal and direct reduced iron are used with the volatilization of zinc metal. Fig. 17 (d) shows the reduction
as raw materials for steel production. product obtained after reduction at 1150
C. It can be seen that the
grain size of the aggregate is the largest, and there is still no metal
lead phase. The analysis results show that the brighter region is
4.1. Characteristics of direct reduced iron mainly sintered metal iron, the gray and black region are mainly
FeO, silicon oxide, calcium oxide and magnesium oxide. Fig. 17
Although there are many reports on pyrometallurgical treat- (e)e(h) are SEM images of carbon-containing EAFD pellets (made
ment of EAFD, the reports on the characteristics of directly reduced with petroleum coke) before and after reaction at the same tem-
iron and zinc-rich dust is little, and the characteristics of recovered perature. Combined with chemical analysis and XRD analysis. It
molten metal products have not been reported. Buitrago et al. shows that the reduction products of the two reductants at corre-
(2018) studied the morphology and composition of reduction sponding temperatures are not much different. However, the
products obtained by Waelz rotary kiln process reducing EAFD with strength test results show that the green pellets prepared by carbon
carbon powder and petroleum coke, respectively. The results show powder as reducing agent and the pellets reduced at various tem-
that the hematite in EAFD raw materials will be converted into perature conditions show better mechanical properties, with an
magnetite below 700
C, metal lead will be reduced at about average difference of about 4 N. At the same time, the reaction rate
800
C, and then zinc ferrite will be decomposed to obtain ZnO and with carbon powder as reducing agent is faster than that with
Fe2O3 when the temperature is higher than 800
C. Valuable metals petroleum coke.
such as iron, zinc and lead will be gradually separated with the Ye et al. (2020) studied the process of recovering direct reduced
occurrence of carbothermal reduction reaction, and temperature is iron from EAFD by microwave. The experimental results show that
the most important factor controlling the chemical reaction rate the recovery rate of total iron is 87.36%, the metallization rate of
(Yunos et al., 2019). Fig. 17 (a)-(d) are SEM images before and after iron in the reduction product is 94.7%, and the iron concentrate
reaction of carbon-containing pellets made of EAFD and carbon obtained after magnetic separation is 91.32%, which meets the re-
powder. The microscopic morphology before the reaction is shown quirements of direct reduction iron. The products after reduction at
in Fig. 17 (a), and it can be clearly seen that the dust particles are 950
Ce1100
C were characterized by XRD, EDS and SEM. Fig. 18
independent of each other and distributed evenly. Fig. 17 (b) shows (a) is a SEM photograph of the product obtained after the mixture
Waelz oxide obtained after reduction of carbon-containing EAFD is heated at 950
C for 15 min. It can be seen that the fine iron grains
pellets at 800
C. The dust particles basically disappear at high are surrounded by darker unreduced phases (such as FeO and
temperature, and the reduction products gradually form aggre- Fe3O4) and gangue components. When the reaction temperature
gates. The detection results show that the substance in the middle rises to 1050
C, the iron grain size becomes obviously larger as
bright area is gradually growing metal lead. Fig. 17 (c) shows Waelz shown in Fig. 18 (b), which shows the importance of temperature to
oxide obtained after reduction at 1050
C. It can be seen that the the reduction reaction. As shown in Fig. 18 (c), that SEM photograph
products of each phase further agglomerate and grow up, and the

Fig. 18. Microstructures of the materials after reduction. (a): At 950
C; (b): At 1050
C; (c): At 1100
C; (d): SEM-EDS analysis of the briquettes after reduction at 1100
C (Ye et al.,
2020).

18
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 19. SEM images of EAFD reduction products. (aeb): Blast furnace sludge with carbon content of 62.2 wt% as reducing agent; (ced): Blast furnace sludge with carbon content of
24.9 wt% as reducing agent (Omran and Fabritius, 2019).

of the reduction product obtained at 1100
C show that the iron reduction product is greatly weakened and the peak of zinc oxide
grains gradually join into one piece and the unreduced part is completely disappears.
decreased. Fig. 18 (d) is the EDS analysis of the reduction product at Comparing the characterization and analysis results of dust
1100
C. The results show that the impurity elements such as Ca, Mg residues from various pyrometallurgical process, it can be seen that
and Si disappear at this temperature, and the gloomy region is the when the operating temperature is greater than 1050
C, metal lead
slag phase composed of oxides such as MgO, MnO and Fe2O3. starts to be separated from the material system. When the tem-
Omran and Fabritius (2019) reported a microwave reduction perature is higher than 950
C, the reaction temperature is the most
process (1100 W, 20 min) for recovering the medium-zinc important factor affecting the reduction reaction. In addition,
(Zn ¼ 19.84 wt%, Fe ¼ 23.70 wt% from Outokumpu Tornio steel compared with other reducing agents, the carbon-containing EAFD
plant, Finland.) and high-zinc (Zn ¼ 35.76 wt%, Fe ¼ 23.50 wt% from pellets obtained by using carbon powder as reducing agent have
Ovako Imatra, Finland.) dust by using blast furnace sludge with better mechanical strength and faster reaction rate. The grade of
different particle sizes as reducing agent. The SEM characterization iron concentrate obtained by pyrometallurgical recovery of EAFD
results of reduction products of medium-zinc and high-zinc EAFD can reach 91.32%, meeting the requirements of direct reduction of
are shown in Fig. 19. As shown in 19 (a) (b), the blast furnace sludge iron. Especially, FeeCreNi alloy with high added value can be ob-
with particle size greater than 250 mm (carbon content 62.2 wt%) is tained when recovering some medium and low-zinc EAFD con-
used as reducing agent. As shown in 19 (c) and (d), the blast furnace taining nickel, chromium and manganese metals.
sludge with carbon content 24.9 wt% is used as reducing agent.
Chemical analysis shows that the removal rate of zinc in each 4.2. Characteristics of zinc-rich dust
reduction product reaches 84.27%e96.06%, and the contents of
lead, chlorine, sodium and potassium are significantly reduced. It The highest volatilization rates of zinc and lead in pyrometal-
can be seen from SEM images that the reduction products are lurgical process of EAFD can reach 99.6% and 92.9%. When the
composed of spherical and slender grain aggregates. Combined reduction temperature exceeds 910
C, metal zinc will volatilize,
with XRD analysis and EDS analysis, it is determined that the main while lead is often volatilized in the form of PbCl2, which are often
images of each reduction product are metallic iron (about 35e39 wt recovered together. According to different recovery processes, zinc
%), calcium ferrite, and calcium silicate. The calcium ferrite may be recovery products are also different. Usually, the separated zinc is
produced by the reaction of zinc ferrite and calcium oxide in EAFD. volatilized and then oxidized again in an oxidation chamber to be
As is shown in Fig. 19 (c) that the nickel-rich (2e3 wt%) ferroalloy collected in the form of zinc oxide, and zinc is also obtained by
phase was detected in the product, and manganese-rich calcium directly condensing zinc vapour through inert gas. These products
ferrite aggregates are also observed in Fig. 19 (b). It can be seen from are collectively referred to as zinc-rich dust.
Fig. 19 (d) that the ferrite grains and part of the grains are sintered, There are three crystal structures for ZnO: hexagonal wurtzite
while XRD analysis also shows that the peak of zinc ferrite in each structure, cubic sphalerite structure and cubic rock salt (NaCl type).
19
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

Fig. 20. SEM pictures of the Zn-containing products. (aeb): SEM images of ZnO fibers (Shen et al., 2007); (c): ZnO needles shape structure; (d): ZnO cross-sectional topography
(Buitrago et al., 2018); (g): SEM image; (h): TEM image; (i): HRTEM image of volatilized matter Zn (Yunos et al., 2019).

Under natural environment, the most thermodynamically stable medium-zinc and low-zinc. Among them, the zinc content of
€
structure is wurtzite (Ozgür et al., 2005). Due to the influence of high-zinc and medium-zinc EAFD is very high (from 8 wt% to 40 wt
process conditions, reactant concentration, pH and other factors %), but the iron content is relatively low (from 17 wt% to 37 wt%).
(Moezzi et al., 2012), the generated zinc oxide has a variety of The low-zinc EAFD has low-zinc content (<8 wt%), but relatively
morphology, including needle-like (see Fig. 20 a-b) (Shen et al., high iron content (from 19 wt% to 49 wt%), and also contains a
2007), cluster-like (see Fig. 20 e-f) and so on. The typical needle- certain amount of Cr (average content 8.1 wt%) and Ni (average
like zinc oxide structure was identified by Buitrago et al. As content 3.5 wt%).
shown in Fig. 20 (c), white sheet around the pellet and small white It is feasible and relatively mature to treat EAFD to produce iron
needles on the support wire was present on the SEM photograph of and zinc-rich dust by pyrometallurgical direct reduction process,
the reduction product obtained by reducing the EAFD at 800
C in but the ring problem of rotary kiln process, high energy con-
the Waelz kiln process. EDX analysis verified that the needle-like sumption (4.0e6.4 GJ$ton1) of rotary hearth furnace process and
substance is ZnO. As shown in Fig. 20 (d), this fact is also verified small treatment capacity of Primus process are all factors restrict-
by the hexagonal structure observed at higher multiples. These ing the development of direct reduction process. High grade zinc-
residual ZnO may be due to the low reaction temperature or low gas rich dust and FeeCreNi alloy can be obtained by smelting reduc-
flow rate, which leads to the reduction of zinc not being separated tion process. Due to its advantages of high process temperature,
out of the reaction system in time, while when the reaction tem- complete reaction, no dioxin emission, less pollution in the pro-
perature is 1050
C, no ZnO is found around the reduction product. duction process and the like, the high-efficiency comprehensive
Ye et al. (2020) used microwave process to reduce EAFD and utilization of EAFD is realized. In particular, ESRF process with
characterized the collected zinc-rich dust. SEM images of the electric arc furnace as the core equipment, recovering EAFD to
product in Fig. 20 (g) show that the grains are hexagonal crystal prepare FeeCreNi alloy and zinc-rich dust is a promising process.
system structure, and the unit cell size is mostly less than 2 mm. In The metallization rate of direct reduced iron in EAFD products
Fig. 20 (i) the position and intensity of the ring in diffraction show treated by pyrometallurgy is generally above 70%, and the direct
that the crystal structure of the product is typical polycrystalline reduced iron obtained by Primus process can be stabilized above
structure. Fig. 20 (h) is a HRTEM photograph of the sample. The 90%. The zinc content of the zinc-rich dust collected from the
intervals of lattice stripes are 0.259 nm, which is consistent with medium-high-zinc EAFD recovered by pyrometallurgical process is
the (100) plane of metal zinc. Combined with XRD analysis junction 50 wt% to 70 wt%. The molten metal obtained by recovering low-
of the product, it can be inferred that the grain is metal zinc. From zinc EAFD contains FeeCreNi alloy with high added value. How-
the characterization results, it can be seen that the zinc-rich dust ever, the research and report on the characteristics of this kind of
recovered by different processes various a lot. The main component products are few at present. Moreover, the serious problems of
of the product recovered by Waelz process is ZnO powder, while refractory erosion and comprehensive utilization of furnace top gas
the product recovered by microwave method is pure metal zinc. are the problems that need to be solved urgently. Much research
needs to be done in these aspects.
5. Conclusion and prospect It is worth mentioning that, if the coal-based direct reduction
and smelting reduction process are combined to develop a new
EAFD has extremely fine particle size, great specific surface area, EAFD treatment process, the recycling process will be greatly
complex chemical composition and phase composition. These shortened and the smelting energy consumption will be reduced.
characteristics lead to the easy spread of EAFD in the air, seriously Coal-based direct reduction recovery of EAFD can obtain zinc-rich
affecting human life and health. Moreover, heavy metals such as Cd dust with high added value and high temperature direct reduc-
and Pb in EAFD will seep into the ground after piled up for a long tion iron. If the high-temperature direct reduced iron is directly
time and being washed by rainwater, resulting in permanent un- charged into the smelting furnace for reduction and melting, the
derground water pollution and irreversible soil pollution. However, smelting time will be greatly saved and the smelting energy con-
on the other hand, there are a large number of valuable metals in sumption will be reduced. Finally, the high-temperature gas
EAFD, such as Zn and Fe, which are often stored in the form of zinc generated by reduction and melting can be introduced into the
ferrite, zinc oxide and iron oxide. According to the different zinc direct reduction equipment for combustion, thus providing the
content, EAFD can be divided into three categories: high-zinc, heat and reducing agent for direct reduction, which will greatly

20
J. Wang, Y. Zhang, K. Cui et al. Journal of Cleaner Production 298 (2021) 126788

improve the utilization rate of gas and further reduce the smelting using electric arc furnace (eaf) dust containing zinc for waelz process. Materia
23, 2.
energy consumption.
Buse, R., Mombelli, D., Mapelli, C., 2014. Metals recovery from furnaces dust: waelz
process. Metall. Ita. 106, 19e27.
Author contributions Buzin, P.J.W.K., Heck, N.C., Vilela, A.C.F., 2017. EAF dust: an overview on the in-
fluences of physical, chemical and mineral features in its recycling and waste
incorporation routes. J. Mater. Res. Technol. 6, 194e202.
The manuscript was written through contributions of all au- Canbekte, Z., 2015. A New Method for Leaching of Electric Arc Furnace Dust (EAFD)
thors. Y.Y. Zhang: Conceptualization, Investigation, and Supervi- with Sulphuric Acid.
Caravaca, C., Cobo, A., Alguacil, F.J., 1994. Considerations about the recycling of EAF
sion. Y.Y. Zhang and Jie Wang: Writing original draft and image
flue dusts as source for the recovery of valuable metals by hydrometallurgical
processing. Jie Wang, K.K. Cui, and T. Fu: Validation, Resources, processes. Resour. Conserv. Recycl. 10, 35e41.
Investigation, Writing - review & Editing. Jie Wang and J. Gao: Chairaksa-Fujimoto, R., Maruyama, K., Miki, T., Nagasaka, T., 2016. The selective
Verification and Modification. Jie Wang, S. Hussain, and T.S. alkaline leaching of zinc oxide from Electric Arc Furnace dust pre-treated with
calcium oxide. Hydrometallurgy 159, 120e125.
AlGarni: Visualization, Writing - review & Editing. All authors have Cheng, G.J., Xue, X.X., Liu, J.X., Jiang, T., Duan, P.N., 2016. Reduction kinetics and
given approval to the final version of the manuscript. mechanism of pellets prepared from high chromium vanadiumetitanium
magnetite concentrate. Trans. Inst. Min. Metall., Sect. C 126, 125e132.
Cheng, T.W., 2003. Combined glassification of EAF dust and incinerator fly ash.
Declaration of competing interest Chemosphere 50, 47e51.
Coronado, M., Andre s, A., Cheeseman, C.R., 2016. Acid gas emissions from structural
The authors declare that they have no known competing clay products containing secondary resources: foundry sand dust and Waelz
slag. J. Clean. Prod. 115, 191e202.
financial interests or personal relationships that could have da Silva, M.C., Bernardes, A.M., Bergmann, C.P., Teno rio, J.A.S., Espinosa, D.C.R., 2008.
appeared to influence the work reported in this paper. Characterisation of electric arc furnace dust generated during plain carbon steel
production. Ironmak. Steelmak. 35, 315e320.
de Araújo, J.A., Schalch, V., 2014. Recycling of electric arc furnace (EAF) dust for use
Acknowledgments in steel making process. J. Mater. Res. Technol. 3, 274e279.
de Vargas, A.S., Masuero, A.B., ^ Vilela, A.C.F., 2006. Investigations on the use of
This work was supported by the National Key R&D Program of electric-arc furnace dust (EAFD) in Pozzolan-modified Portland cement I (MP)
pastes. Cement Concr. Res. 36, 1833e1841.
China (2017YFB0603800 & 2017YFB0603802), and Researchers Dilmac, N., Yo € rük, S., Gülabog lu, Ş.M., 2012. Determination of reduction degree of
Supporting Project Number (RSP-2020/254) King Saud University, direct reduced iron via FT-IR spectroscopy. Vib. Spectrosc. 61, 25e29.
Riyadh, Saudi Arabia. Emery, T.S., Raghupathi, P.A., Kandlikar, S.G., 2018. Bubble growth inside an evap-
orating liquid droplet introduced in an immiscible superheated liquid. Int. J.
Heat Mass Tran. 127, 313e321.
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