Accepted Manuscript

Pyrometallurgical recycling of electric arc furnace dust

Xiaolong Lin, Zhiwei Peng, Jiaxing Yan, Zhizhong Li, Jiann-Yang Hwang, Yuanbo
Zhang, Guanghui Li, Tao Jiang

PII: S0959-6526(17)30351-7

DOI: 10.1016/j.jclepro.2017.02.128

Reference: JCLP 9054

To appear in: Journal of Cleaner Production

Received Date: 22 July 2016

Revised Date: 25 January 2017

Accepted Date: 17 February 2017

Please cite this article as: Xiaolong Lin, Zhiwei Peng, Jiaxing Yan, Zhizhong Li, Jiann-Yang Hwang,
Yuanbo Zhang, Guanghui Li, Tao Jiang, Pyrometallurgical recycling of electric arc furnace dust,
Journal of Cleaner Production (2017), doi: 10.1016/j.jclepro.2017.02.128

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Highlights

There exists a major environmental issue concerning electric arc furnace dust.

The recent advances in pyrometallurgical recycling of the dust are reviewed.

Principles, advantages and limitations of different processes are discussed.

Technical challenges for dust recycling and potential solutions are pointed out.
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1 Pyrometallurgical recycling of electric arc furnace dust

2 Xiaolong Lina, Zhiwei Penga,*, Jiaxing Yana, Zhizhong Lia, Jiann-Yang Hwangb,

3 Yuanbo Zhanga, Guanghui Lia, Tao Jianga

5 a School of Minerals Processing and Bioengineering, Central South University,

6 Changsha, Hunan 410083, China.

7 b Department of Materials Science and Engineering, Michigan Technological

8 University, Houghton, MI 49931, USA.

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*Corresponding author. Tel.: +86 731 88877656; fax: +86 731 88830542.
E-mail address: zwpeng@csu.edu.cn (Z. Peng).
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21 Abstract: Electric arc furnace (EAF) dust is an important secondary resource which

22 contains multiple metallic elements, such as zinc, lead, iron, chromium and cadmium.

23 Recycling of EAF dust is not only favorable to increasing economic potential of the

24 dust by recovering these valuable metals, but also of benefit to solving disposal and

25 environmental problems caused by the heavy metals (e.g., lead, chromium and

26 cadmium) entrained in the dust. Among the existing processes and those under

27 development, pyrometallurgical routes are considered the primary choice for

28 processing of EAF dust because of its high potential metal recovery, easy treatment of

29 residue and relatively short flow sheet. In this paper, the authors reviewed the

30 chemical and physical properties of EAF dust and its thermodynamic characteristics

31 in pyrometallurgical processing, followed by an in-depth discussion of a variety of the

32 pyrometallurgical processes for recycling of the dust, including Waelz kiln process,

33 rotary hearth furnace (RHF) process, PRIMUS process, OXYCUP process, coke-

34 packed bed process, Ausmelt process, electric smelting reduction furnace (ESRF)

35 process, Plasamadust process, plasma-arc process, Elkem multi-purpose furnace

36 (EMPF) process, submerged plasma process, pig iron zinc oxide (PIZO) process,

37 flame reactor process, thermal plasma reduction process, microwave processing, solar

38 thermal reduction process, iron bath smelting process, calcification process and

39 halogenation process. Particular attention is devoted to specific technical challenges

40 emerging in the pyrometallurgical processing of EAF dust and to the corresponding

41 potential measures for improving the dust recycling by promoting the processing

42 efficiency with elimination of secondary hazardous pollutants.

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43 Keywords: Electric arc furnace dust, Recycling, Pyrometallurgical process, Zinc, Iron,

44 Hazardous pollutants

45

46 1. Introduction

47 With the rapid development of steelmaking industry, the global crude steel

48 production reached a stage of 1.623 billion tons in 2015 (World Steel Association,

49 2016). The crude steel production is accompanied by a large amount of dust/sludge,

50 slag, wastewater and exhaust gas which pose a great threat to both environment and

51 human health (Mo, et al, 2015; Gomes, et al., 2016; Pan, et al., 2016). The steel plant

52 dusts are an important by-product of the steelmaking industry with output accounting

53 for about 10% of the crude steel production (Dutra et al., 2006). As a representative

54 type of steel plant dust, electric arc furnace (EAF) dust has an output equal to

55 approximately 1%-2% of the charge in a typical EAF operation (Dutra et al., 2006). In

56 2014, the global EAF dust output soared to 8.764 million tons. This dust generally

57 contains up to 40 wt.% zinc (Nolasc-Sobrinho et al., 2003) and 50 wt.% iron (Orhan,

58 2005; Salihoglu and Pinarli, 2008). It is also accompanied with a variety of harmful

59 heavy metals, e.g., Pb, Cr and Cd (Pinarli, 2008), and thereby frequently categorized

60 as one of most troublesome and hazardous waste being difficult to store and transport

61 (Lis et al., 2015). For disposal of the dust, landfilling offers a simple solution (Donald

62 and Pickles, 1996). However, it not only causes accumulation of heavy metals in the

63 groundwater and soil under the impact of rain, posing harm to animals and plants as
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64 well as human survival environment, but also results in a waste of resources as

65 valuable elements such as zinc and iron are not recovered.

66 In view of the potential economic and environmental benefits of EAF dust, it is

67 of importance to develop appropriate approaches for treatment of the dust. The

68 emergent processing methods can be classified into three categories, namely

69 pyrometallurgical processes, hydrometallurgical processes and chemical

70 stabilization/vitrification (Donald and Pickles, 1996). The principle of

71 hydrometallurgical approaches, for example, the classical ZINCEX process (Díaz et

72 al., 2001) and EZINEX process (Castro and Marques, 2001), is to leach metal oxides

73 (ZnO, PbO, etc.) from the dust in either an acidic (Hilber et al., 2003) or an alkaline

74 solvent (Havlík et al., 2005). These processes usually place stringent requirements on

75 the leaching apparatus due to the lixiviants of relatively high concentration (Havlík et

76 al., 2006). The acidic lixiviants, such as sulfuric acid (Li et al., 2010), have good

77 recovery of zinc (Leclerc et al., 2002), but may simultaneously cause secondary

78 wastes (Pickles, 2009) and dissolution of iron (e.g., up to 45% even when diluted

79 sulfuric acid (acid normality =3 N) was used) (Oustadakis et al., 2010) which hinders

80 the subsequent operations such as zinc electrowinning (Tsakiridis et al., 2010).

81 Compared with acidic solvents, alkaline lixivants (e.g., sodium hydroxide) are more

82 selective with respect to multiple metals (Bakkar, 2014). The alkaline route may

83 achieve better results technically and economically, with less generation of residue

84 (Palencia et al., 1999). The shortcoming of alkaline leaching is the undesirable

85 leaching of lead (Youcai and Stanforth, 2000). Because of these problems, particularly
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86 the strongly pH dependent leaching of zinc and lead (Kumpiene et al., 2008), complex

87 operations and multiple steps are often necessary for hydrometallurgical processes to

88 improve recovery of the metals (Tang and Steenari, 2016), especially for leaching of

89 the dust with a high content of slightly soluble zinc ferrite (Youcai and Stanforth,

90 2000). Furthermore, severe leachate contamination issues may occur arising from the

91 halogens (Ruiz et al., 2007) and the other components in the EAF dust (Oustadakis et

92 al., 2010). The principle of chemical stabilization/vitrification (e.g., the Oregon

93 process), on the other hand, is to mold EAF dust into lump by direct sintering or by

94 sintering with chemical additives, e.g., CaCO3, Na2CO3 and SiO2 (Kavouras et al.,

95 2007), or by stabilization with addition of lime (Pereira et al., 2001), other wastes

96 such as blast furnace slag, coal fly ash or aluminum cement after mixing, molding and

97 compacting (Salihoglu and Pinarli, 2008). Because this method is solely used for

98 generating impermeable substrate which encapsulates dust particles for stabilization

99 of hazardous components in dust, it does not sufficiently take into account the

100 recovery of metals of economic interest, therefore representing a waste of resources

101 (Pickles, 2008). Unlike hydrometallurgical processes and chemical

102 stabilization/vitrification, the principle of pyrometallurgical processes is to recover the

103 metals, primarily based on carbothermic reduction or other thermal reactions (e.g.,

104 calcification and halogenation) (Guo et al., 2010). Although hydrometallurgical

105 processes and chemical stabilization/vitrification method have relatively lower energy

106 consumption (Mauthoor et al., 2014), pyrometallurgical processes, featured by high

107 potential metal recovery, easy treatment of residue and short flow sheet, are deemed
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108 the preferential option for recycling of EAF dust and remain the only ones which have

109 reached commercialization (Huaiwei and Xin, 2011).

110 Currently, recognition in recycling of the dust via pyrometallurgical processing

111 is still incomplete despite the progress of treatment of EAF dust in the past decades.

112 The aim of the present study is to present a critical review of pyrometallurgical

113 processes for recycling of EAF dust. The chemical/physical characteristics of the dust

114 and its thermodynamic characteristics in pyrometallurgical processing are provided,

115 followed by a detailed review of the mainstream and recently developed routes for

116 recovery of metal values from the dust. Lastly, the technical challenges to the

117 progress of the pyrometallurgical processing of EAF dust are summarized and

118 corresponding potential/promising measures are expounded with aim to offer a useful

119 guideline for sustainable recycling of the dust.

120

121 2. Methods

122 This review is designed to summarize and evaluate recent advancements in the

123 recycling of EAF dust via various pyrometallurgical processes. A number of

124 commercial websites, scientific journal articles, proceedings papers and reports were

125 selected and reviewed. The literature search was carried out using the most important

126 and commonly used databases, such as Web of Science, Scopus, SciFinder and

127 Google Scholar. At first, the following specific keywords were chosen: electric arc

128 furnace dust, dust recycling, carbothermic reduction, pyrometallurgical process, zinc,

129 lead, iron and hazardous pollutant. Subsequently, the abstracts were carefully
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130 examined before the publications were determined based on the criteria which

131 correlate to the paper’s objective and fit its scope. Particularly, the authors appraised

132 studies: 1) characterizing physiochemical properties of EAF dust; 2) exploring

133 reaction mechanisms during pyrometallurgical processing; 3) providing sustainable

134 approaches with crucial technologies parameters; and 4) addressing future prospects

135 of pyrometallurgical processes without secondary hazardous pollution.

136

137 3. Chemical and physical characteristics of EAF dust

138 The chemical and physical characteristics of EAF dust are the starting point in

139 the definition of a suitable recycling process. These characteristics mainly include

140 chemical composition, phase composition, particle size distribution, density and

141 moisture content, microstructural morphology and thermal property.

142 3.1. Chemical composition

143 EAF dust is produced when zinc-bearing scrap is remelted in an electric arc

144 furnace. The type of scrap processed in an EAF has a substantial effect on the dust

145 composition and properties. The components of EAF dust originate from vaporized

146 and subsequently oxidized non-ferrous metals, metal and slag constituents formed due

147 to the explosion of CO gas bubbles at the slag-gas interface, and from low density

148 furnace additions, such as carbon and lime which are captured by the off-gas handling

149 system (Pickles, 2009). The prevailing elements in EAF dust are zinc, iron and

150 calcium. Other less prevalent elements include sodium, potassium, manganese and

151 silicon. The dust also contains hazardous lead, chromium and cadmium. According to
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152 zinc content, it can be divided into 3 categories: low zinc dust (< 4 wt.%), medium

153 zinc dust (4%-20 wt.%) and high zinc dust (> 20 wt.%) (Lis et al., 2015), as shown in

154 Table 1. The zinc content in the dust increases with declining iron content. This trend

155 is attributed to the reactions of zinc oxide with iron oxides in EAF, which elevate the

156 content of iron in the EAF dust by forming ferrites. For the other major element in the

157 EAF dust, calcium, its content remains relatively constant because it is primarily

158 introduced to EAF by addition of flux which can be controlled exactly in practice.

159 The above-mentioned minor elements in the dust are mostly originated from the feed

160 of EAF. Most of them enter the dust because of the high operating temperature of

161 EAF and their relatively low boiling temperatures. Due to the complicated occurrence

162 of these elements, prior treatments before pyrometallurgical step, such as In-Process

163 Separation (Ma, 2011; Ma, 2016), may be implemented to enrich beneficial elements

164 and to reduce concentrations of harmful elements in the dust.

165 3.2. Phase composition

166 The phase composition of EAF dust is summarized in Table 2. The main phases

167 of EAF dust are zinc oxide (zincite), zinc ferrite (franklinite), ferric oxide (hematite),

168 ferrous-ferric oxide (magnetite), calcium oxide (lime), calcium carbonate (calcite),

169 calcium-iron silicate (hedenbergite), etc. The hazardous metals, such as lead and

170 chromium, are mainly present in the form of oxides (e.g., cerusite and chromite). The

171 occurrences of these elements are consistent with their contents in EAF dust shown in

172 Table 1. The formations of the major phases are a result of intensive reactions

173 between zinc, iron and calcium species which are involved in the EAF smelting. The
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174 minor phases, such as lead and chromium oxides, are present due to volatilization and

175 subsequent oxidation or entrainment of relevant metals.

176 3.3. Particle size distribution

177 The formation process of the EAF dust implies that the dust would be a complex

178 powdered waste composed of fine-grained particles. The dust particle size usually

179 ranges from 0.1 to 100 μm (Ranitović et al., 2014). Fig. 1 shows the particle size

180 distribution of an EAF dust sample (Oustadakis et al., 2010). It is observed that the

181 dust had two main size fractions, namely a very fine-grained portion (0.1-1 μm) and a

182 coarser portion (1-100 μm). Half of the dust particles were below 19.3 μm, and

183 approximately 90% of the particles were less than 100 μm. It is worth noting that the

184 particle size distribution of EAF dust is closely associated with its moisture content.

185 The large solid agglomerates in EAF dust are often a result of long period storage

186 (Huaiwei and Xin, 2011).

187 3.4. Density and moisture content

188 Table 3 lists the density and moisture content of EAF dust collected from two

189 different locations. The apparent density of the dust varies significantly, depending on

190 the source position, while the real density remains relatively constant. In general, EAF

191 dust has a very low moisture content (< 1 wt.%).

192 3.5. Microstructural morphology

193 Fig. 2 shows an electron micrograph of dispersed EAF dust particles (Simonyan

194 et al., 2015). The friability and porosity of the surfaces of the dust particles and some

195 aggregations between the particles are clearly observed (Badger and Kneller, 1997).
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196 The spherical morphology confirms that the dust formation is a result of slag

197 (Mantovani et al., 2002) and metal ejection by CO bubble bursting on the surface of

198 the bath (Guézennec et al., 2004). Dendritic structures may exist within the spherical

199 particles, comprising an iron-chromium spinel and a slag matrix composed of silicon,

200 calcium, iron, aluminum, magnesium and oxygen (Nolasc-Sobrinho et al., 2003).

201 Additionally, a number of metal-oxygen structural forms may appear, as demonstrated

202 by the match of metal and oxygen distribution in accumulations in Fig. 3 (Sofilić et

203 al., 2004) which shows the elemental distribution images of oxygen, zinc, magnesium,

204 aluminum, silicon, sulfur, lead, calcium, manganese, iron and copper.

205 3.6. Thermal property

206 The thermal stability of EAF dust can be revealed by thermogravimetric analysis

207 (TGA). Fig. 4 shows the TGA profile of a EAF dust sample (26.66 wt.% Zn) at a

208 ramp rate of 10 °C min-1 under N2 atmosphere (Al-Harahsheh et al., 2014). According

209 to the diagram, there existed three steps for the mass loss. The first mass loss event

210 started at 136 °C with the maximum mass loss rate occurring at 175 °C,

211 corresponding to evaporation of entrained free water and chemically adsorbed water

212 (e.g., water bound to the metal chlorides). The second mass loss had an onset

213 temperature of 380 °C with the maximum mass loss occurring in the range 630-700

214 °C, essentially attributed to the vaporization of metal chlorides (e.g., ZnCl2). The final

215 mass loss event initiated at a temperature of 750 °C, and the loss was assigned to the

216 vaporization of zinc metal generated due to reduction of zinc oxide by free carbon

217 (2.2 wt.%) present in the dust.

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218

219 4. Thermodynamics concerning pyrometallurgical processing of EAF dust

220 The principle of pyrometallurgical processing of EAF dust is to extract valuable

221 metals such zinc, iron, lead, etc, from the dust, essentially dependent on carbothermic

222 reduction (e.g., Waelz kiln process ), calcification (e.g., calcification process) or

223 halogenation (e.g., chlorination process). The Gibbs free energy expressions of main

224 reactions involved in pyrometallurgical processing of EAF dust were determined by

225 the FactSage™ software [version 7.0, Thermofact/CRCT (Montreal) and GTT-

226 Technologies (Aachen), Federal University of São Carlos] and the results are

227 summarized in Table 4.

228 As shown in Table 4, zinc oxide, ferrous oxide, lead oxide, chromium trioxide

229 and cadmium oxide can be reduced into metallic forms at relatively low temperatures

230 (< 1000 °C, see reaction temperature in Table 4 at which the corresponding reaction

231 takes place) in spite of their endothermic nature. This fact partially supports recycling

232 EAF dust via pyrometallurgical processes. After reduction, zinc, lead and cadmium

233 will evaporate because of their high vapor pressures at the EAF operating

234 temperature. The metal vapors can then be condensed, separated and recovered using

235 a condenser system. Conversely, iron and chromium will be retained in the residue

236 after thermal reduction. The iron-rich residue from reduction of dust, especially from

237 the low-zinc dust, is eligible for reclamation. This residue can be used directly, or

238 after simple treatment, as a qualified secondary raw material for steel production.
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239 It should be emphasized that most of the existing pyrometallurgical processes are

240 based on carbothermic reactions. The metal oxides in EAF dust are reduced by either

241 carbon or carbon monoxide. Compared with solid carbon, carbon monoxide has better

242 reducing ability, demonstrated by its low reduction temperatures in Table 4. As a

243 matter of fact, many of the metal extraction processes involve use of both reducing

244 agents (Zhang et al., 2000). This statement is particularly true when the dust has a

245 high carbon content or carbonaceous materials are added as reducing agent. In such

246 case, the reduction initially depends on the degree of contact between carbon and the

247 dust particles where the solid/solid reaction occurs, and there are very low vapor

248 partial pressures of CO and metals (e.g., zinc, lead and cadmium). With gradual

249 consumption of carbon in reduction of the metal oxides, however, the contact area

250 between carbon and metal compounds decreases. On the contrary, the CO partial

251 pressure increases steadily with involvement of Boudouard reaction. Consequently,

252 the solid/solid reduction reaction becomes more difficult and the reduction reactions

253 between CO and the metal oxides in the dust dominate the extraction process. Hence,

254 for recycling of EAF dust via carbothermic reduction, accelerating gasification of

255 carbon and mass transfer of CO is crucial and is worthy of extensive exploration.

256

257 5. Pyrometallurgical processes for recycling of EAF dust

258 For treatment of EAF dust, many pyrometallurgical processes have been

259 developed or are under development. In the present study, the Waelz kiln process,

260 rotary hearth furnace (RHF) process, PRIMUS process, OXYCUP process, coke-
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261 packed bed process, Ausmelt process, electric smelting reduction furnace (ESRF)

262 process, Plasamadust process, plasma-arc process, Elkem multi-purpose furnace

263 (EMPF) process, submerged plasma process, pig iron zinc oxide (PIZO) process,

264 flame reactor process, thermal plasma reduction process, microwave processing, solar

265 thermal reduction process, iron bath smelting process, calcification process and

266 halogenation process are covered and reviewed. A brief comparison of these

267 pyrometallurgical processes is shown in Table 5. It should be mentioned that before

268 the pyrometallurgical step, zinc enrichment is also important and sometimes very

269 necessary. In fact, a few relevant methods have been developed. For example, the

270 EAF dust injection technology, in which the dust is injected into EAF, considerably

271 reduces the total amount of dust. Most of the zinc in the injected dust returned to the

272 dust fraction in the furnace atmosphere whereas the rest dissolves in the slag. The zinc

273 accumulates in the EAF filter dust which therefore becomes more attractive for metal

274 recovery without negative effect on dust emissions or steel quality (Evans and Hogan,

275 1987; Jensen and Wolf, 1997; Tsubone, et al., 2012). Isozaki et al. (2002) proposed a

276 method to separate and recover iron and zinc from EAF exhaust gases using a coke

277 bed filter and a zinc condenser to prevent the formation of the dust, eliminating the

278 need for its costly recycling processes. The exhaust gas from EAF passes through the

279 coke bed filter maintained at 1000 °C. The zinc and lead vapors after reduction are

280 collected and separated in the downstream condenser, which rapidly cools the gas

281 from 1000 °C to about 450 °C. Condensed zinc and lead metals are collected in liquid

282 state at the bottom of the condenser, while iron and slag components are collected in
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283 the filter. Ma (2011) proposed a radical new approach, the In-Process Separation

284 (IPS) technology, in which zinc is removed from the EAF off-gas before it reacts with

285 iron-containing particles to form the franklinite phase in the combustion chamber. The

286 dust collected in the baghouse filters can be sent directly to the crude zinc oxide

287 treatment plant as it will no longer contain Fe. However, this technique requires

288 implementation in each individual EAF plant. It may be impossible to collect the

289 starting product from a larger area to treat a large amount of dust simultaneously

290 (Suetens, et al., 2014).

291 5.1. Waelz kiln process

292 Among all high-temperature metal recovery processes, the dust processed by the

293 Waelz kiln accounts for about 75% of the total treated EAF dust globally (Mager et

294 al., 2000). Fig. 5 shows a simplified flow chart of Waelz kiln process (Mager et al.,

295 2003). Initially, a homogeneous mixture of EAF dust, reductant and flux is prepared

296 in the pellet form. The pelletized material is sent into the Waelz kiln for drying and

297 preheating by the countercurrent-flow kiln gas. In the reaction zone, the metal oxides

298 are reduced at about 1100-1200 oC to volatilize zinc and lead from the charge in the

299 form of metal vapors. By controlling admission of air at the kiln outlet end, zinc and

300 lead in the gas phase are oxidized again and formed as Waelz oxide, while the

301 metallic iron in the charge is re-oxidized and then constitutes a byproduct called

302 Waelz slag (Coronado, et al., 2016). Meanwhile, the process heat liberated can be

303 effectively utilized in the charge. In the process, chlorine and alkalis volatilize

304 together with the heavy metals. The dust-laden off-gas will be treated in a
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305 downstream off-gas unit for purification. The rotary kiln furnace is used to treat

306 Waelz oxide to refine zinc with elimination of lead, cadmium and chlorides (Morcali

307 et al., 2012).

308 The Waelz kiln process is considered to be a relatively mature process for

309 recycling of EAF dust in spite of several disadvantages. The major shortcoming of

310 this process is associated with the remained zinc and lead in the Waelz slag where

311 iron is not sufficiently enriched after separation of zinc in the form of vapor,

312 indicating waste of iron units. This problem becomes more serious when the process

313 produces high amounts of slag (about 700-800 kg t-1 of charged dust) (Antrekowitsch

314 et al., 2015). Also, as the major aim of this process is to recover zinc, the zinc

315 concentration of the dust must be higher than 16 wt.% to ensure economics of the

316 process (Leclerc et al., 2002). High energy consumption is another drawback of this

317 process due to its strict requirements on the operation temperature of units (Mishra et

318 al., 2002). Moreover, it is an off-site process in which high tipping and shipping fees

319 ($80-$125 ton-1) have to be applied (Sun et al., 2008), adding cost.

320 5.2. Rotary hearth furnace process

321 The rotary hearth furnace (RHF) process is an important coal-based direct

322 reduction method for dust recycling (Lu and Huang, 2003) and has been practiced in

323 the steel industry (Oda et al., 2006). Fig. 6 shows the primary flow chart of RHF

324 process for treatment of EAF dust (Tsutsumi et al., 2010). By this process, the mixture

325 of the dust, reducing agent and additives is first used for pelletizing (Wu et al., 2013).

326 The green pellets/briquettes prepared are sent into the moving RHF and heated to
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327 1000 oC in its heating zone. After they enter into the reaction zone of RHF, a number

328 of high temperature chemical reactions take place and the overall temperature can

329 reach up to 1300 oC. During the process, the metal oxides are reduced to the

330 corresponding metallic forms. Zinc and lead are separated from the pellets in the form

331 of vapor and subsequently enter into the exhaust pipe. The metal vapors are oxidized

332 to zinc oxide and lead oxide, respectively, along with the movement of waste gas, and

333 collected by the dust collector in the form of soot. During the process, alkaline metal

334 chlorides are removed simultaneously. The iron oxides are reduced into direct reduced

335 iron (DRI) under strong reducing atmosphere and the percent reduction of DRI

336 reaches up to 90% in 15-20 min (Kuwauchi and Barati, 2013).

337 The RHF direct reduction process is deemed effective in processing EAF dust

338 containing appreciable amounts of iron, carbon, zinc, lead and alkalis. With the

339 process, high-grade zinc product and DRI can be produced instead of slag. It was

340 therefore claimed that this process may be commercially and environmentally

341 superior to the Waelz kiln technology (Nakayama and Taniishi, 2011). The iron

342 metallization degree, zinc removal ratio and alkali metals (K and Na) removal ratios

343 may exceed 75%, 95%, and 80%, respectively, for the reduced pellets/briquettes

344 under the condition of the molar ratio of carbon to oxygen equals 1.0 at 1230 °C for

345 15 min. The downside of this process, however, is due to the requirement for the

346 charge. Until recently, the RHF process was only suited for recycling EAF dust with

347 low zinc content (< 5 wt.%) (Suetens et al., 2014) although this technology has been

348 reengineered to overcome operational problems such as zinc oxide blockages at

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349 higher zinc content, mainly associated with low compressive strength of the

350 pellets/briquette which may result in substantial amount of broken pellets and fines

351 which must be returned to the pelletizing step, thereby lowering the process

352 productivity. Moreover, due to the large initial investment in equipment,

353 the economic benefits of the process have to be enhanced further, especially at the

354 early stage of its operation.

355 5.3. PRIMUS process

356 The PRIMUS technology involves use of multi-hearth furnace for metallization

357 of non-agglomerated finely dispersed EAF dust (Frieden et al., 2001), as shown in

358 Fig. 7. The furnace consists of a cylindrical chamber on a vertical axis, with multiple

359 superimposed or stacked annular compartments between which the hearth floors/roofs

360 are constructed of refractory bricks which form self-supporting levels with openings.

361 In practice, a mixture of pulverized coal and EAF dust is charged at the uppermost

362 hearth and transported from one hearth to the next and from the center to the wall and

363 back with the aid of scrapers. The processing temperature can be elevated from

364 ambient temperature to 1100 °C by the combustion of coal in burners and by the

365 secondary combustion of CO formed during reduction. At high temperatures, zinc and

366 lead compounds are reduced to their metallic forms, evaporated, re-oxidized by the

367 furnace gas, removed from the furnace through the exhaust port and collected in the

368 gas-cleaning system (bag filter) with the recovery degree of 95%. Meanwhile,

369 alkaline compounds are vaporized and captured. At the bottom of the furnace DRI or

370 iron concentrate with degree of metallization 90-95% is discharged, cooled and used
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371 for BF smelting or EAF steelmaking (Kurunov, 2012). In this way, separation of iron

372 from zinc and lead and other elements such as sodium and potassium as well as

373 chlorine is realized.

374 The PRIMUS process is featured by unprepared and low-cost feed, rapid

375 reduction of metal oxides due to intensive stirring and heating, high efficiency with

376 relatively low process temperatures (1000-1100 °C) and excellent quality products,

377 including highly metallized DRI (> 90%) and highly concentrated zinc oxide which

378 enable selective extraction of the zinc (Roth, et al., 2001; Suetens, et al., 2014). The

379 downside of this process is associated with the corrosion of furnace due to both rapid

380 stirring and evaporation of alkaline compounds during reduction. Meanwhile, to keep

381 good kinetic conditions for the charged feed, the furnace has a restricted size which

382 restrains its productivity, as indicated in Table 5.

383 5.4. OXYCUP process

384 The OXYCUP process, developed by Kuttner GmbH& Co., melts self-reducing

385 briquettes by vibropressing EAF dust, sludge and scale generated in steelmaking with

386 a cement binder in a cupola operated with an oxygen-enriched blast (5-15% of oxygen

387 enrichment) (Fisch and Kesseler, 2006; Holtzer, et al., 2015), as shown in Fig. 8. The

388 briquettes are charged into the furnace with fluxes and large pieces of scrap (up to 1

389 m). Coke and carbon fines are used as fuels. In particular, coke provides most of the

390 energy source for the furnace and guarantees the permeability of stock column. At

391 low temperatures (c.a. 500 °C), portions of metallic iron are formed on the external

392 surface of briquettes. This coating grows and protects briquette against decomposition
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393 beyond 1000 °C when the direct reduction by carbon contained in briquettes initiates.

394 In contrast to blast-furnace smelting, most iron in the OXYCUP process is reduced by

395 carbon in the briquettes at 900-1400 °C in a short period of time (20-30 min)

396 (Kurunov, 2012). At temperatures above 1450 °C briquettes completely convert into

397 spongy iron, which is melted together with the metallic charge loaded to the furnace.

398 Molten metal containing 4 wt.% carbon is tapped continuously at 1500 °C. Overall,

399 the process produces “zero waste” (Holtzer, et al., 2015). The resulting pig iron of

400 precisely known quality is delivered to the steel plant. The slag is granulated and the

401 cleaned top gas rich in CO is used as a fuel. The top dust is recycled into briquettes

402 and sold as zinc concentrate (crude zinc oxide) with sufficiently high zinc content

403 (e.g., 30 wt.%).

404 The OXYCUP process shows a good combination of the function of melting in

405 traditional cupolas and that of reduction in BF, thereby useful for both high- and low-

406 zinc burdens. It is expected to remedy some major defects of traditional processes

407 such as Waelz kiln process (Holtzer, et al., 2015). In general, this process produces

408 hot metal with lower cost than that from BF. It is also an environmentally friendly

409 approach for EAF dust treatment as emissions of sulfur oxides, nitrogen oxides,

410 dioxins and furans are below the allowable values. Like those in BF smelting

411 (Hryniewicz and Janewicz, 2008; Magdziarz et al., 2011; Magdziarz et al., 2015), the

412 prepared charge should have sufficient strength to sustain the reduction process.

413 However, information concerning the reduction of the briquettes composed of EAF

414 dust in the process is insufficient. To improve the furnace operation, more efforts
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415 should be spent on illustrating the reduction process in the furnace in association with

416 the physicochemical properties of the charge.

417 5.5. Coke-packed bed process

418 The coke-packed process is a smelting reduction process using a shaft furnace

419 with a coke packed bed for recycling of steelmaking dust (e.g., EAF dust) developed

420 by Kawasaki Steel Corp (Itaya, et al, 1990). The furnace is featured by installation of

421 two stage tuyeres, namely upper and lower tuyeres (Fig. 9). Fine raw materials (EAF

422 dust, flux and coke) without agglomeration are injected through the upper tuyeres and

423 then melted instantly in the raceway inside the shaft furnace. Because of efficient heat

424 exchange between the ascending gas and the descending coke in the furnace, a high

425 temperature and intensively reducible region is formed between the upper and lower

426 tuyeres. The melted oxides in the dust are easily reduced to metals as they drip

427 through the high-temperature coke-paced bed. When the molten metals (e.g., iron,

428 chromium and nickel) and slag drop to the hearth, high-vapor-pressure elements

429 including zinc and lead are vaporized and extracted through the furnace top. As

430 shown in Table 5, the process has three products: crude zinc oxide, molten metal, and

431 slag. By treating a typical EAF dust containing 27.7 wt% zinc, 25.0 wt.% iron and

432 3.22 wt.% lead, it was found that zinc and lead were concentrated in the crude zinc

433 oxide (60 wt.% zinc and 6.2 wt.% lead) and their contents in the metal (0.005 wt.%

434 zinc and 0.001 wt.% lead) and the slag (0.01 wt.% zinc and 0.001 wt.% lead) were

435 very low (Hara, et al., 2000).

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436 The coke-packed process has advantages of efficient separation of various metals

437 such as zinc, lead and iron. However, the smelting reduction consumes a huge amount

438 of heat. In practice, it is necessary to elevate the temperature to over 1550 °C at the

439 level of the lower tuyeres, which supply the majority of heat, to completely reduce

440 metal oxides. Also, it is crucial to prevent the zinc adhesion on the wall of the furnace

441 top. Further efforts should be made to maintain top gas temperature and CO2/CO in

442 the region where zinc vapor is stable (Hara, et al., 2000).

443 5.6. Ausmelt process

444 EAF dust can be treated using Ausmelt technology (Hughes et al., 2008). In this

445 technology, the granulated mixture consisting of EAF dust, reducing agent and

446 additives is sent into the Ausmelt furnace from a lid plug without drying (Hughes et

447 al., 2008). The powdered coal and fuel gas are injected into welding pool by a spray

448 gun to maintain the temperature of furnace at about 1300 oC. The melting temperature

449 of EAF dust usually ranges from 1250 to 1400 oC. After zinc oxide and lead oxide are

450 reduced to their metallic forms at about 1100 oC, the metals will volatilize and re-

451 oxidize to their corresponding oxidized forms due to reactions with the air above the

452 molten pool (Zhou, 2002). These oxides are collected in a bag filter chamber before

453 further treatment and recycling (Matusewicz and Mounsey, 1998).

454 The advantage of the process is ascribed to its good aerodynamic condition

455 which can promote the reduction of zinc and lead oxides and volatilization of zinc and

456 lead but hinder the reduction of iron oxide by controlling the atmosphere and

457 temperature. This feature allows potential reduction in the energy consumption of the
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458 dust treatment with the removal ratio of zinc amounting to 65%-75% (Yin, 1998).

459 However, the relatively low purity of zinc soot in the process and insufficient

460 productivity due to complex bed operations restrain its development.

461 5.7. ESRF process

462 The ESRF process simply uses an electric furnace for material heating and oxide

463 reduction (Nakayama, 2012). Fig. 10 shows the primary flow chart of ESRF process

464 for treatment of EAF dust. In this process, a mixture of agglomerated EAF dust, coke

465 and limestone as material charge is loaded into the furnace. Carbon monoxide and Zn

466 vapor in the exhaust gas are oxidized in the combustion chamber (a simple vertical

467 cylinder) with water-cooled and partially refractory-lined wall which prohibits the

468 adhesion of softened dust and facilitates cleaning. Powders of iron oxide and carbon

469 settled at the bottom of the combustion chamber are recycled to the ESRF. Hot

470 exhaust gas containing much crude zinc oxide and chlorides is withdrawn from the

471 combustion chamber and quickly cooled through the multi-tube gas cooler for

472 recovering the particles in the bag-house. The temperature of the gas cooler is

473 controlled to solidify the chlorides on the vertical tube surface. By removing the

474 chlorides a good zinc oxide recovery from crude zinc oxide with 65-82 wt.% zinc

475 oxide can be achieved. High-carbon pig iron (3.44 wt.% carbon) is returned to arc

476 furnace steel mills. Slag with 0.44 wt.% zinc and 0.03 wt.% lead is cooled down

477 slowly in a slag pot to generate crystallized structure with very low leaching values of

478 heavy metals such as zinc, lead and cadmium, simplifying downstream disposals such

479 as landfill or use as aggregate for construction (Nakayama, 2012).

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480 The ESRF process is characterized by the use of sole electrical energy for

481 heating, melting and reduction without any fuel and by the low carry-over of charged

482 dust and high zinc oxide content (over 70%) in crude zinc oxide. When ESRF is

483 installed in an EAF plant, energy is saved because molten pig iron can be directly

484 charged into the EAF, without use of a casting machine to make ingots. Meanwhile,

485 high gas temperature of over 1250 °C completely decomposes dioxins and other

486 organic substances in EAF dust. No hazardous materials remain in the slag. The

487 disadvantage of this process is the high energy cost. Thermal energy of the hot

488 exhaust gas is often not actively used, and only a portion of energy is used for

489 preheating the charged material. It is the main reason why the process was once

490 abandoned. New ESRF process is expected to meet the economic requirements when

491 recovered metal prices increase and environmental regulation becomes more severe.

492 5.8. Plasamadust process

493 The Plasmadust process is carried out in a coke-filled shaft furnace equipped

494 with D.C. non-transferred plasma devices (e.g., three 6 MW plasma generators)

495 (Schoukens et al., 1993). These devices are mounted on the tuyeres of the shaft

496 through which EAF dust, pulverized coal, fluxes and superheated plasma gas are

497 injected. The high temperatures (around 2500 °C in the raceway formed in front of

498 each tuyere) and low oxygen partial pressure in the furnace enable the reduction of

499 iron and chromium oxides at 1400-1600 °C, which is difficult for many traditional

500 fuel-air based processes, e.g., the Waelz kiln process. Molten iron with various

501 metallic species and a nonhazardous slag are tapped at the lower part of the furnace.
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502 One of the main shortcomings of this process is the relatively low zinc content (about

503 20 wt.%) in the crude zinc oxide produced from the process which needs to be

504 processed further in a high-temperature furnace, such as Waelz kiln.

505 5.9. Plasma-arc process

506 There are two alternatives of plasma-arc process for treatment of EAF dust,

507 namely the Tetronics and Enviroplas processes (Schoukens et al., 1993; Goff and

508 Denton, 2004; Denton, et al., 2005). The former process was developed by Tetronics

509 Research and Development (TRD) in the UK in the late 1970s (Schoukens et al.,

510 1993). The feeds, including EAF dust and coke fines, are charged through ports in the

511 roof of a cylindrical D.C. plasma-arc furnace. The temperature of the furnace is

512 maintained by supplying electric energy via a graphite electrode in the center. During

513 the process, the metals produced by reduction of oxides of zinc, lead and cadmium are

514 vaporized, condensed and captured in a zinc splash condenser. A non-hazardous slag

515 is formed and tapped periodically from the furnace while off-gases are withdrawn

516 from the furnace continuously. The Enviroplas process is another plasma-arc process

517 developed by Mintek based on the carbothermic and metallothermic reduction of

518 metal oxides in the EAF dust at 1400-1600 °C in a DC plasma arc furnace (Assis,

519 1998). The Tetronics and Enviroplas processes are differentiated by charging practice.

520 In the Enviroplas process, the feed is transferred to the furnace via the central hole of

521 the graphite electrode while in the Tetronics process it is charged through the ports

522 located in the roof of the furnace. Feeding through the hollow graphite electrode in

523 the Enviroplas process offers a series of advantages, including direct delivery of feed
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524 into the high temperature reaction zone under the electrode, rapid absorption of EAF

525 dust into the molten slag, and reduced contamination and elutriation or carry-over of

526 the feed due to minimized interaction of the leaving vapor products with feed

527 materials falling down from feed ports in the roof. The ferro-alloys produced contain

528 relatively small quantities of sulfur and phosphorus (about 0.06 wt.% and 0.04 wt.%,

529 respectively) which enable further steelmaking. The slag has less than 0.1% of the

530 zinc input, while the fumes produced contain high grade of zinc oxide (on average

531 56.3 wt.%). Due to its large energy requirement, this process has a much smaller

532 capacity, in comparison with the Waelz kiln process (Table 5).

533 5.10. EMPF process

534 The EMPF process for treatment of EAF dust is based on a three-phase slag-

535 resistance furnace characterized by advanced electrode seal designs, gas tight bodies

536 and roofs, and fully cooled slag zones using plate coolers which generate a frozen-

537 slag (freeze) lining (Kennedy et al, 2009). The furnace has high intensity ranging

538 from 300-400 kW m-2 of hearth area or approximately 300-1000 kW m-3 of slag

539 volume. The 10 MW EMPF built at Laclede Steel, Alton (IL) has an annual designed

540 capacity of 40 kt of EAF dust (Schoukens et al., 1993; Kennedy et al, 2009). This

541 process shares several similarities with the plasma-arc process. For example, like the

542 Tetronics process, vaporized products withdrawn from the furnace are captured in a

543 zinc splash condenser. The main differences are the use of a three-phase slag-

544 resistance furnace instead of a D.C. open-arc furnace and the application of briquettes

545 instead of un-agglomerated feeds. Compared with the Enviroplas process which has
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546 the inherent advantages of a D.C. plasma-arc furnace over an A.C. slag-resistance

547 furnace, the EMPF process has relatively higher electrode consumption, lower-

548 symmetry heat distribution and more complex operation control.

549 5.11. Submerged plasma process

550 The submerged plasma zinc-fuming process uses electric plasma torches (plasma

551 generators) to supply process heat and good mixing conditions to the slag bath into

552 which a mixture of pelletized EAF dust, petroleum coke and flux is fed continuously

553 (Verscheure, et al., 2005; Verscheure, et al., 2007a), as shown in Fig. 11. Inside the

554 plasma torches, the cold blast air is transformed into a high enthalpy plasma gas

555 which is mixed with natural/petroleum gas and injected into the slag bath. The solid

556 feed dissolves into the molten bath and blast gases react with the slag and reductant.

557 Zinc and other volatile metals fume off. Above the bath, the fume is post-combusted

558 with secondary air, and the resulting off-gases and solid zinc oxide particles are

559 removed from the smelting vessel. After the post-combustion the off-gas is further

560 oxidized with air in a radiation chamber and treated in an electrostatic precipitator to

561 recover zinc oxide. Part of the heat generated in the post-combustion is transferred

562 back to the slag bath to increase energy efficiency of the process. The outputs of the

563 process are an iron, calcium and silica-rich slag phase, a matte phase, crude zinc oxide

564 powder (55-65 wt.% zinc) and off-gas (Verscheure, et al., 2007a).

565 In the submerged plasma process, the carbon and heat requirements of the

566 process are separated. The molar ratio of carbon to oxygen (C/O) and electrical power

567 can be independently adjusted to optimize the performance of the furnace. The use of
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568 submerged plasmas also enables high slag bath temperatures (around 1300 to 1400

569 °C) which promote high zinc-fuming rates. A key feature of the process is the use of

570 high temperature freeze linings (a layer of bath material that protects the furnace wall,

571 formed on the reactor wall backed by the water-cooled steel furnace shell) to contain

572 this slag bath, designed through the control of bath chemistry with use of dolomite

573 flux. Using such freeze linings promotes maximum operation temperatures of

574 conventional slag fumers which are restrained by highly superheated aggressive

575 fayalite slags, in spite of increased enthalpy losses to the water cooling system due to

576 the high superheat of the slags. The design of these freeze linings is crucial for the

577 technical and economic feasibility of the process. The use of supplementary heat

578 supplied by the plasma torches helps to maintain high bath temperatures and the

579 application of high liquidus temperature slags provides stable freeze linings to keep

580 integrity of the bath wall. These features and the reactor design lead to higher zinc-

581 fuming rates than those achievable using conventional zinc-fuming processes. The use

582 of hydroelectric power in the plasma offers the opportunity of lowering the

583 environmental impact of the process through reduced greenhouse gas emissions.

584 Additional work is required to simultaneously optimize slag composition and process

585 performance while ensuring vessel integrity via model development (Verscheure, et

586 al., 2007b). The challenge is to engineer or select a slag chemistry which will provide

587 a stable protective furnace lining and also minimize heat losses through the furnace

588 shell.

589 5.12. PIZO process

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590 The PIZO process uses a continuous channel induction furnace as the primary

591 unit for processing of EAF dust (Bratina and Lenti, 2008). The furnace contains a

592 molten iron bath which serves as a heat sink to rapidly heat the charged material, a

593 briquetted mix of EAF dust and reductants. Under high temperature conditions (1300-

594 1500 °C), reduction of oxides of zinc, lead and cadmium proceeds quickly, followed

595 by that of iron and other metals. Zinc, lead and cadmium are vaporized and re-

596 oxidized. The metal oxide dust is collected as crude zinc oxide in a baghouse system.

597 Iron and some other metals which enter into the molten bath are removed by rotating

598 the furnace forward and pouring the bath through a teapot spout into a receiving ladle.

599 The iron product may be saleable after pouring into a pig machine or used directly as

600 hot metal. Remaining materials, including silica, calcium, magnesium and aluminum,

601 produce a molten slag which can be removed from the furnace by rotating the furnace

602 backward and used as a slag modifier or road aggregate.

603 The channel induction furnace fits in with the needs of continuous feed of raw

604 materials to produce zinc, iron and slag products which are removed continuously or

605 semi-continuously. The inductors on the furnace serve as an efficient device for

606 providing energy for the process. All three distinct products of the process, pig iron,

607 crude zinc oxide and slag, are saleable. Approximately 95% of the input iron is

608 recovered as pig iron with a much higher market value than the typical iron/slag mix

609 generated from a Waelz kiln (The PIZO® Advantage, 2016). Meanwhile, there is very

610 low loss of iron product to the crude zinc oxide (< 1.5 wt.% iron in the oxide) and to

611 the slag (Bratina and Lenti, 2008). Hence, the process reduces the loss of iron and
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612 provides a better feed material for downstream zinc processing operations. For further

613 improvement of the PIZO process, up-scaling its capacity with minimized energy

614 consumption and environmental impact is ongoing.

615 5.13. Flame reactor process

616 The flame reactor process involves use of a flame reactor (a water-cooled

617 vertical cylinder, diameter 0.6 m × height 3 m) having an upper combustion zone and

618 a lower smelting zone for EAF dust treatment (Orhan, 2005). In the combustion zone,

619 CO is produced by the partial combustion of natural gas with oxygen-enriched air in a

620 cyclone burner at the top of the reactor. The hot reducing flame (> 2000 °C) travels

621 down to the smelting zone, where the dust is injected pneumatically with feed rates of

622 1-2 t h-1 of EAF dust. Due to the rapid reactions at high temperatures (about 1600 °C),

623 the average retention time of the dust in the flame reactor is only half a second. Like

624 many of the approaches for management of EAF dust, the oxides of zinc, lead and

625 cadmium in the flame reactor process are reduced to their metallic forms. The metals

626 undergo vaporization and re-oxidization. Lastly, a crude zinc oxide is collected in a

627 bag filter for subsequent metal extraction in electrothermic zinc plants. The molten

628 slag generated is tapped continuously from the reactor for sale or disposal (Assis,

629 1998). Overall, this process has a simple operation, despite a relatively low efficiency

630 which is mainly restricted by the combustion of fuel in the flame reactor.

631 5.14. Thermal plasma reduction process

632 A representative plasma technology is the Scan Dust AB (Li, 2012). In this

633 technology, flue gas is decomposed into the gas atoms or particles by the electric
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634 current on the electrode (copper) produced by the high temperature (approximately

635 3000 oC) (Simonyan et al., 2015). The gas atoms or particles generated are burning in

636 the combustion chamber, making the flame center temperature reach as high as 20000

637 oC. When the granulated mixture consisting of EAF dust and reducing agent is sent

638 into the plasma furnace, a series of reduction reactions occur at once due to the high

639 temperature in the reaction zone. In this process, zinc oxide and lead oxide are

640 reduced to the vapors of zinc and lead which are condensed as liquid metals outside

641 the furnace condenser. The mixture of metal vapors is gradually separated in the

642 condenser because of the different boiling points of the metals. Meanwhile, iron is

643 enriched in slag and discharged from the bottom of furnace.

644 A study by Best and Pickles examined the feasibility of recovering metals of

645 values from EAF dust containing 24.8 wt.% zinc using a 24 kVA AC plasma arc

646 furnace under CO atmosphere between 1000 and 1400 °C with reaction ratio of 1-8 g

647 L-1 (dust feeding rate to CO flow rate) and dust feeding rate of 50-150 g min-1 (Best

648 and Pickles, 2001). The volatile elements (zinc, lead, cadmium, potassium and

649 sodium) were collected in a condenser, whereas the remaining elements (iron and

650 chromium) constituted a slag phase. The zinc recoveries reached up to 97%, and the

651 removal of lead closely approximated that of zinc, accomplished by either reduction

652 of lead oxide which leads to evaporation of lead or volatilization of lead-bearing

653 species, namely lead sulfide, lead chloride and lead oxide. The cadmium in the dust

654 was found to be almost totally recovered in the condensate during cooling of the off-

655 gas phase. Simultaneously, exceeding 90% of the alkalis (potassium and sodium)
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656 were removed primarily due to the volatilization of the salts. In addition, greater

657 potassium removal was achieved associated with the higher vapor pressure of

658 potassium chloride compared to sodium chloride (Magdziarz et al., 2015). Most of

659 chromium (>93%), on the other hand, was remained in the iron-rich phase because of

660 high stability of chromium oxides and low equilibrium partial pressure of chromium-

661 bearing compounds. In principle, the iron-rich slag could be reclaimed to the

662 steelmaking circuit.

663 The plasma technology provides more effective recovery of zinc and iron, in

664 comparison with other approaches such as the Waelz kiln process. It can be used in

665 large or small operations because of its compact equipment, short payback period of

666 investment, high efficiency, environmental friendliness, operation flexibility and

667 special advantage of recovering the valuable metals such as chromium (Huaiwei and

668 Xin, 2011). Currently, the main problem of this technique is ascribed to the

669 determination of the optimum parameters of the reactionary zone and velocity of

670 process for maximum extraction of zinc and lead. This issue is particularly important

671 for scaling up the plasma process because it is operated at high temperatures,

672 implying great energy consumption. Further, there exists a relatively strict

673 requirement for the property of feed. In general, highly-dispersed powdered EAF dust

674 is preferred because it fits the needs of the technology.

675 5.15. Microwave processing

676 Microwave processing of materials, featured by volumetric heating, selective

677 heating and non-thermal effects (Peng, 2012), is an advanced alternative to

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678 conventional methods because microwave energy is absorbed at the molecular level

679 and heat can be generated inside materials (Peng and Hwang, 2015). Processing EAF

680 dust under microwave irradiation has fast reaction rate, large zinc removal ratio and

681 high iron metallization degree, thereby receiving increasing attention. Sun et al.

682 investigated the zinc removal and metallization of iron as a function of microwave

683 time and carbon addition at microwave power of 1100 W (Sun et al., 2008). Because

684 the mixture of EAF dust and carbon powders (20 wt.%) was heated well in the

685 microwave field, the removal of zinc was near completion in only 12 min, with the

686 highest zinc removal ratio and iron metallization degree approaching 99.2% and

687 100%, respectively. Zhou et al. (2015) also assessed the performance of using

688 microwave energy for recycling of EAF dust. It was found that for the sample with 16

689 wt.% graphite irradiated by 10 kW microwaves for 10 min, the removal ratio of zinc

690 varied between 80% and 90% and the metallization ratio of iron ranged from 40% to

691 60%. This result was partially attributed to microwave heating which overcame the

692 barrier of traditional heating model characterized by inward heat transfer. It was also

693 closely correlated to the magnetic ferrites contained in the dust which served as strong

694 microwave absorbers and to the lower processing temperatures associated with

695 smaller reaction activation energy (Zhou et al., 2015).

696 Obviously, microwave processing offers an efficient choice for treatment of EAF

697 dust. It is actually a result of the good microwave absorbance of the materials used in

698 processing (carbonaceous materials) and of the components in the dust (e.g., ferrites)

699 (Peng, 2012). Hence, an in-depth exploration of microwave absorbing properties of

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700 iron-bearing and zinc-bearing phases (magnetite, franklinite, etc.) as well as reducing

701 agents like coal/coke (Peng et al., 2016; Peng et al., 2017), which depend on their

702 compositions and structures (Sebastian et al., 2015), will allow further enhancement

703 of metal recovery and treatment efficiency with great environmental friendliness via

704 microwave processing.

705 5.16. Solar thermal reduction process

706 Solar thermal reduction is a clean technology which can be used to recycle EAF

707 dust and other waste materials in a sustainable manner. According to Schaffner et al.

708 (Schaffner et al., 2003), it employed a high-flux solar furnace equipped with a solar

709 chemical receiver-reactor in which the carbothermic reduction of EAF dust was

710 performed using concentrated solar energy. For solar thermal reduction, a solar

711 concentrating facility was an essential prerequisite. Such facility could offer up to 50

712 kWth of thermal radiative power at peak radiative flux of 11000 kW m-2 by

713 incorporating an array of 10 high-pressure Xe arcs coupled with ellipsoidal specular

714 reflectors (Tzouganatos et al., 2013). The reduction relied on the solar reactor

715 consisting of an upper cavity and a lower cavity, separated by a 170 mm-diameter 5

716 mm-thick SiC-coated graphite plate (Tzouganatos et al., 2013). The upper cavity

717 received concentrated solar irradiation which passed through a 65 mm-diameter

718 circular aperture with a 2 mm-thick quartz window. The lower cavity was an

719 octagonal enclosure (diameter 135 mm× height 170 mm) which served as the reaction

720 chamber containing a packed bed of solid reactants. With this arrangement, the

721 concentrated solar radiation was efficiently adsorbed by the top of the packed bed.
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722 The technical feasibility of solar thermal reduction has been demonstrated in the

723 temperature range 847-1127 °C with both batch and continuous modes of operation

724 (Schaffner et al., 2003), which extracted up to 99% and 90% of the zinc in the EAF

725 dust, respectively. The condensed off-gas products were found to be mainly

726 constituted by zinc, lead and chlorine. By maintaining the O2 concentration in the

727 furnace below 2 vol.%, the zinc oxide presence could be minimized.

728 The solar thermal energy was also used for purification of Waelz oxide

729 containing 55-65 wt.% zinc in oxidic form from the EAF dust processed in the Waelz

730 kiln process and for extraction of zinc by carbothermic reduction (Tzouganatos et al.,

731 2013). It was shown that by clinkering the oxide at above 1265 °C using a 10 kWth

732 packed-bed solar reactor, the content of impurities (e.g., chlorides and fluorides) in

733 the oxide could be reduced below 0.1 wt.%. The clinkered oxide was reduced under

734 solar irradiation using biochar as CO2-neutral reducing agent between 1170 °C and

735 1320 °C, which yielded 90 wt.% zinc in the condensed product. Incorporation of

736 continuous or semi-continuous feeding of reactants and removal of products could

737 further improve product yield and thermal efficiency.

738 The most prominent advantage of solar thermal reduction process is the

739 minimization of emissions of greenhouse gases and other pollutants. For further

740 development of the process, particular attention should be paid to optimizing solar

741 reactor with maximum thermal efficiency and chemical reaction. In fact, the thermal

742 efficiency of solar system is relatively low (usually <10%) although it increases with

743 reactor temperatures and feeding rates (Schaffner et al., 2003). To obtain high thermal
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744 efficiency and chemical conversion, it is of importance to match the energy

745 absorption rate with the feeding rate of reactants and the kinetics of the reaction.

746 5.17. Iron bath smelting process

747 The iron bath smelting process was designed to produce hot zinc, lead and iron

748 economically from EAF dust at low capacity with direct use of coal (particularly non-

749 coking coal). By this process, the valuable metals can be recovered through forming

750 the alloy with the melting iron which can be easily separated from the innocuous slag.

751 Chen and Gammal (2000) investigated zinc recovery from EAF dust by bath smelting

752 reduction in a furnace using inert gas as protective gas. For zinc and lead

753 volatilization, a certain amount of pure iron was first melted at 1400 °C in a graphite

754 crucible into which a mixture of EAF dust and flux with various CaO/SiO2 mass ratios

755 was charged. After the desired time the slag and metal generated were removed, while

756 secondary dust was collected at the roof of furnace. The main reactions between metal

757 oxide in slag and carbon in melt are shown in Table 4. It was found that the smelting

758 reduction of (FeO) with carbon in the melt was 10-100 times faster than that with

759 solid carbon or CO gas, revealing precisely the advantage of the process. Both the

760 volatilization degrees of (Zn) and (Pb) exceeded 99% at 1400 °C. After metal-slag

761 separation, iron was enriched in the metallic part in which the zinc and lead contents

762 decreased from 22% and 1.12%, respectively, to less than 0.005%.

763 Apart from carbon, silicon can also be used for ferrous oxide reduction and zinc

764 recovery. Grillo et al. (2014) reported that it was possible to recover 98% of the Fe in

765 EAF dust and the secondary dust collected after the test had a high level of zinc (68
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766 wt.%) at 1500 °C. Of interest is the ferrous oxide was reduced by carbon in a lesser

767 and slower extent than it was reduced in the presence of silicon. The slag was featured

768 by low ferrous oxide and zinc oxide contents, implying great potential for complete

769 recovery of these oxides.

770 It is evident that the bath smelting reduction process has a good separation of the

771 main metals in the EAF dust treatment. However, due to the strict requirement for the

772 reduction temperature (1400-1500 °C) which must be maintained to enable melting of

773 the reaction system (Pickles, 2010) the high energy cost of the process constitutes a

774 major obstacle to its further development.

775 5.18. Calcification process

776 The calcification process aims at recovering zinc oxide from EAF dust by

777 addition of calcium carbonate (Itoh et al., 2008) or lime (Chairaksa-Fujimoto et al.,

778 2015). According to Itoh et al. (Itoh et al., 2008), the dust and calcium carbonate were

779 initially mixed at an appropriate ratio and then pressed into the 10 mm diameter 1.5 g

780 tablet under the pressure of about 400 MPa before heating in air for a desired holding

781 time at temperature of 900 oC or 1100 oC. In the reaction zone, the franklinite, the

782 main zinc-bearing component in EAF dust reacted with the calcium oxide, producing

783 zinc oxide and calcium ferrite (Ca2Fe2O5). Because of the remarkable difference

784 between the magnetic susceptibility of zinc oxide and that of calcium ferrite, they

785 could be separated under a high gradient magnetic field. It was reported that 95% of

786 the zinc oxide in the dust was recovered in spite of approximately 6 wt.% calcium

787 ferrite contamination. Another benefit of this process is the preferential volatilization
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788 of lead, chloride and fluorine in the EAF dust (Chairaksa-Fujimoto et al., 2015). Most

789 of lead and chloride were removed preferentially at temperatures below 900 °C,

790 whereas complete removal of fluorine occurred above 1000 °C in the presence of

791 calcium oxide. In the process without addition of calcium oxide, on the other hand,

792 the evaporation of halogens and lead in the dust began at temperatures higher than

793 560 °C and drastically increased at about 900 °C (Chairaksa-Fujimoto et al., 2016).

794 Most of the chloride, fluorine and lead were removed from the remaining dust at 1100

795 °C (Chairaksa-Fujimoto et al., 2015).

796 The calcification process shows a high recovery ratio of zinc because the

797 majority of zinc oxide and calcium ferrite in the dust can be efficiently separated. The

798 by-product of the process, calcium ferrite, may be used in dephosphorization during

799 the process of steel making. However, in this process, the large addition of calcium

800 carbonate or calcium oxide, e.g., Ca/Fe>1.0 (Chairaksa-Fujimoto et al., 2015), often

801 leads to low zinc oxide yield in magnetic separation and increased contaminants in the

802 Zn-bearing fraction.

803 5.19. Halogenation process

804 The halogenation process is based on the reaction between highly reactive

805 halides (or their derivatives) and non-ferrous metals in the EAF dust, followed by

806 evaporation of the formed metallic halides from the solid residue. It can be divided

807 into two main groups: the chlorination process and the bromination process. Recently,

808 the chlorination process has attracted increasing attention. According to Guo et al.

809 (Guo et al., 2010), EAF dust was first mixed with calcium chloride (CaCl2) powders
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810 as chlorinating agent to prepare a charge with Zn/Ca molar ratio of unity before it was

811 transferred into the hot zone of an electric furnace within flowing purified N2 gas

812 between 875 and 1050 oC. Under this circumstance, zinc, iron and lead were

813 respectively chlorinated to ferrous chloride, lead chloride and zinc chloride by

814 calcium chloride. Due to the high vapor pressures of zinc chloride and lead chloride,

815 they were easy to volatile and remove at low temperatures. Iron, on the other hand,

816 remained in the dust residual phase in the form of oxide. The recovery ratio of zinc

817 could reach 80% in the temperature range from 875 oC to 1050 oC. Fig. 12 shows a

818 schematic of the reaction between zinc ferrite powders and calcium chloride (Guo et

819 al., 2010). It is observed that the zinc ferrite particles were wrapped by the molten

820 calcium ferrite and the chlorination reaction occurred at the solid-liquid interface. The

821 zinc chloride dissolved in the liquid membrane of calcium chloride and volatilized at

822 the interface before the product layer of calcium ferrite was continuously increasing

823 and enriched in the residue for further removal.

824 Apart from calcium chloride, hydrogen chloride (HCl) gas evolved from organic

825 waste (Lee and Song, 2007), such as polyvinyl chloride (PVC), has been utilized a

826 useful chlorinating additive to assess the feasibility of recycling EAF dust for metal

827 extraction (Zhang et al., 2000). During the processing of the mixture of EAF dust and

828 PVC, the metal oxides in the dust were converted to metal chlorides and recovered in

829 the gaseous form (Zhang et al., 1999). The dust served as a viable treating agent for

830 harmless incineration of PVC which, on the other hand, produced hydrogen chloride
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831 through thermal decomposition in recovering metals from waste stream. After water

832 leaching, the metals were separated (Sofilić et al., 2004).

833 Based on a similar mechanism, the bromination process makes use of the

834 reaction between reactive bromide with zinc- and lead-bearing phases in the EAF

835 dust. By this route, Grabda et al. investigated recycling of EAF dust in the presence of

836 bromine-containing plastic waste, namely tetrabromobisphenol A (TBBBPA) and

837 tetrabromobisphenol A diglycidyl ether (TBBPADGE), which released reactive HBr

838 gas during thermal decomposition (Grabda et al., 2014). When the mixture of the dust

839 and TBBBPA/TBBPADGE was compressed into pellets and heated at 550 °C for 80

840 min under oxidizing or inert conditions, high separation of zinc and lead from the dust

841 was achieved. Particularly, in the case of TBBPADGE, a maximum of 85% of zinc

842 and 81% of lead could be recovered.

843 The halogenation process is highly selective in separating metal elements,

844 mainly Zn and Pb, in the dust and meanwhile enriches Fe in the residual phase. With

845 this process, the reaction temperature may be reduced considerably regarding the low

846 boiling points of the metal chlorides or bromides. In addition, the reduction furnace is

847 unnecessary in the process. The biggest concern about this technology, however, is

848 the addition of halides which, as expected, often cause corrosion of apparatus and

849 pose a potential environmental threat in the subsequent operations.

850

851 6. Discussion
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852 As a typical by-product of electric arc furnace steelmaking, EAF dust contains a

853 variety of valuable elements (iron, zinc, lead, etc.). Its chemical/phase composition

854 and fine granularity are compatible with pyrometallurgical recycling. As

855 aforementioned, most of pyrometallurgical processes are based on the carbothermic

856 reduction of metal oxides in the dust, primarily aiming at recovering zinc, lead and

857 iron. Zinc oxide as a main zinc-bearing phase is easy to reduce, while the other major

858 phase, zinc ferrite, must decompose to zinc oxide first under reducing atmosphere

859 before reduction thereafter. Because a significant amount of gaseous zinc can be

860 formed at temperatures above 1000 oC, the effective removal of zinc from EAF dust is

861 feasible at a temperature of 1000-1100 oC. Unlike zinc oxide, the lead oxide starts to

862 reduce to its metallic state at 650 oC and begins to evaporate and convert into a gas

863 phase at 900 oC. As expected, these reduction reactions can be accelerated with

864 increasing temperature. After separation of zinc and lead, iron in the dust is enriched

865 in the residue for further treatment.

866 Based on the above principles, the Waelz kiln process, RHF process, PRIMUS

867 process, OXYCUP process, coke-packed bed process, Ausmelt process, ESRF

868 process, Plasamadust process, plasma-arc process, EMPF process, submerged plasma

869 process, PIZO process and flame reactor process (Table 5) have been successfully

870 used in industry. Meanwhile, some unconventional methods with higher processing

871 efficiency and metal recovery, such as microwave processing and solar thermal

872 reduction process, are being developed for further optimization of treatment of EAF
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873 dust in a more sustainable way, representing future directions of technological

874 innovation and development in pyrometallurgical recycling of the waste.

875 Despite apparent progress in this field, there still exist several technical

876 challenges/problems. One of the most important deficiencies of the current research

877 which, to some extent, restricts the development of technologies for EAF dust

878 treatment is the insufficient exploration of the properties and complex association of

879 occurrence of iron-, zinc-bearing and other minor phases in the dust. For instance, it

880 was shown that zinc oxide could restrain the reduction of iron oxide, but the

881 competing effect of reduction of zinc oxide and iron oxides are not well illustrated

882 based on the both thermodynamic and kinetics analyses (Machado et al., 2006). The

883 activities of these oxides (e.g., zinc oxide and ferrous oxide) may also be decreased

884 apparently due to the existence of spinel phases Fe3-xCrxO4 and ZnFe2O4, which

885 shows the close association of these metals. Secondly, non-ferrous metals, such as Zn,

886 are easy to vaporize and separate from a Fe-rich phase, but they are usually re-

887 oxidized in many processes and, therefore, the gaseous product of the dust processing

888 is often a crude oxide which requires further treatment and thus additional input of

889 energy. Thirdly, because certain non-ferrous metals and hazardous elements remain in

890 the process fume/residue, their disposal may constitute a big puzzle and sometimes

891 pose harsh requirements on operation apparatus. As mentioned above, the majority of

892 the pyrometallurgical processes focus only on recovery of zinc, lead and iron from

893 EAF dust in which other hazardous elements such as chlorine and chromium were not

894 explored adequately (Bruckard et al., 2005).

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895 To tackle the first problem for desirable extraction of these metals, more efforts

896 should be directed to the formation and decomposition of the spinel phases and

897 separation of the metals based on the exploration of properties of the ferrites (Zhang

898 et al., 2000). It was reported that inside the off-gas ducts of EAF the spinel phases

899 such as franklinite forms through a gas-solid reaction starting from pure Fe droplets

900 and Zn vapor (Nedar, 1996). The amount of the spinel phases at room temperature

901 generally decreases with increasing zinc and manganese contents in the dust.

902 Conversely, it increases with increasing iron content. Hence, from the point of view of

903 efficient metal extraction, the first choice for pyrometallurgical processing is to

904 eliminate the formation of spinel phases, which can be achieved by reducing the

905 oxygen potentials, operating EAF under airtight conditions (Nedar, 1996), increasing

906 dust loading, or using additives such as calcium oxide and its derivatives (e.g., CaF2)

907 (de Araújo and Schalch, 2014). It should be pointed out that although the presence of

908 CaO (in the form of lime or calcium carbonate) can thermodynamically reduce the

909 amount of spinel at 1100 °C through the formation of various calcium ferrites (e.g.,

910 CaO.Fe2O3 and 2CaO.Fe2O3) which results in the liberation of zinc oxide and iron

911 oxide, thereby increasing the non-ferrous metal recoveries (Pickles, 2008), the

912 appropriate use of the additive deserves special attention in view of its sensitive dose

913 dependence of relevant phase transformations. Currently, such dependence can be

914 partially revealed by several advanced microscopy technique (Denning, et al., 2016;

915 Payton, et al., 2016). In fact, after all of the ferrite spinel disappears, the amount of

916 zinc oxide remains relatively constant but that of iron oxide decreases as the amount
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917 of calcium ferrite continues to increase. In EAF dust, however, the amount of calcium

918 ferrite is relatively low despite a relative large amount of calcium oxide. This is a

919 result of the slow kinetics of reactions involving solid calcium oxide (Zhang et al.,

920 1999), which warrants extra consideration. From the perspective of decomposition of

921 the spinel phases and separation of the metals, the preliminary thermodynamic

922 analysis of carbothermic reduction of spinel phase implied that relatively high

923 temperatures and low (oxygen) pressure favor high zinc and lead recoveries, while

924 low temperature and relatively high total pressure/high reactant ratio are of benefit to

925 high metallic iron recovery (Wu et al., 2014). Therefore, reducing the total pressure

926 and introducing non-reactive gas may contribute to increased non-ferrous metal

927 recoveries and decreased metallic iron recovery. Further separation of zinc, lead and

928 other non-ferrous metals can be realized by controlling processing temperature and

929 reactant ratios considering the difference in their thermodynamic stability (Pickles,

930 2007).

931 To prevent metal re-oxidation during cooling, it is important to ensure the

932 reducing atmosphere in the whole process using a suitable reducing agent which

933 simultaneously reduces its CO2 footprint. One option is substituting fossil raw

934 materials (e.g., coal and coke) with carbon-neutral ones based on biomass, such as

935 biochar (Griessacher and Antrekowitsch, 2012). This reductant has a high gasification

936 efficiency and faster reduction speed which help to maintain the atmosphere in the

937 reduction process. It is also characterized by very low impurity (e.g., sulfur and

938 phosphorus) contents and carbon neutrality, producing much less pollution to the
 ACCEPTED MANUSCRIPT

939 environment. Obviously, the economics of the new processes involving biomass-

940 based materials depend on many factors, such as biomass availability and price, costs

941 for biomass conversion, effectiveness of the carbon-neutral reducing agent,

942 development of carbon taxes and additional costs arising from environmental

943 legislation in future. Other than solid reducing agents, gaseous reductants including

944 CO and H2 may be employed to prevent the re-oxidation of the metals. It was

945 proposed that by using CO gas as a reducing agent for recycling of EAF dust, an iron-

946 rich residue with an iron grade of 89.9 wt.% and metallization degree over 95% could

947 be obtained, in spite of 0.26% lead and minor amounts of potassium (0.19%) and

948 sodium (0.18%) (Wu et al., 2014). Meanwhile, the zinc dust had over 90%

949 metallization degree of zinc and can be used as raw material in the zinc refinery dust

950 after removal of chlorides (Pickles, 2007). In comparison to CO, the use of H2 gas has

951 additional advantages. For instance, it functions in the minimization of halogens

952 (chlorine and fluorine) in the separated gaseous product after reduction, which

953 simultaneously improves the entire process (Antrekowitsch and Antrekowitsch,

954 2003). Its use and the combined use of both carbon (Pickles, 2007) and H2 are

955 considered to be promising in the thermal reduction of EAF dust (Antrekowitsch and

956 Antrekowitsch, 2003).

957 In pyrometallurgical recycling of EAF dust, the fume (e.g., zinc oxide fume)

958 generated is usually polluted by chlorine and fluorine (Tsugita, 2003), while the

959 residue/slag produced often has a high iron content (Barna et al., 2000) and a small

960 amount of non-ferrous metals such as zinc and lead which can be recycled either in an
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961 electric arc furnace or blast furnace (Peng et al., 2001). For improved disposal of the

962 fume and residue, removal of chlorine from raw dust is essential (Tsubouchi et al.,

963 2010). In fact, the existence of chlorine can cause free dioxins and furans, such as

964 polychloridedibenzodioxines and dibenzofurans (PCDD/F), during the thermal

965 treatment of the dust (Rösler et al., 2014). It was shown that by curbing the chlorine

966 load alone a significant PCDD/F minimization formation can be achieved (Mager et

967 al., 2000). The chlorine content also influences the vaporization behaviors of Zn and

968 Pb. Lead chloride forms a hydroxyl-halide (PbOHCl) and lead chloride carbonate

969 (Pb2CO3Cl2) agglutinative matrix which is hard to remove. In this regard, introducing

970 fresh EAF dust directly to washing process before fuming or processing the dust in H2

971 atmosphere was recommended for chlorine removal (Abdel-latif, 2002). Another

972 option is roasting the dust with CO2 at 600 °C, followed by water washing, to avoid

973 formation of adhesive lead and zinc hydroxide chloride to improve the removal of

974 chloride (Chen et al., 2011). Further dechlorination can be realized by microwave

975 roasting because of strong microwave absorbance of chlorides in the dust compared to

976 zinc oxide. A recent study revealed that when the dust from zinc leaching residue by

977 Waelz kiln volatilizing was roasted under microwave irradiation at 626 °C for 25 min

978 and stirring at 54 rpm, the dechlorination ratio could reach 90.13% (Wang et al.,

979 2014). For removal of fluorine, two approaches were developed, namely fixing

980 fluorine in the by-products as MnF2 or as FeF2 and eliminating fluorine by alkaline

981 washing prior to the treatment of the gases with SO2. Both methods are technically

982 possible and perhaps complementary (Menad et al., 2003). To remove chlorine and
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983 fluorine compounds simultaneously, separating these halides in an oxidizing step at

984 about 1150 °C for 150 min (also known as clinkering) prior to reduction of remaining

985 residue seems reasonable in spite of loss of a small amount of valuable metals (Hung

986 et al., 2012). It was reported that a very high amount of chlorine (>90%) was removed

987 and similar results were obtained for fluorine. Further optimization of halides removal

988 relies on an in-depth exploration of the basic knowledge on the behaviors of relevant

989 elements. In particular, it is necessary to establish a competent thermodynamic

990 database from which the behaviors of halogens and heavy metals (e.g., saturated

991 vapor pressures of heavy metals and their partition in the fume/residue system) as

992 well as their interactions in a specific process can be inferred and identified.

993 From the above discussion, chromium usually retains in the residue due to high

994 stability of the chromium oxides and low equilibrium partial pressure of the

995 chromium-containing compounds over the temperature range from 1000-1400 °C.

996 Hexavalent chromium in the EAF dust has 100-fold more toxicity than trivalent

997 chromium because of its high water solubility and mobility (Hara et al., 2000; Kim, et

998 al., 2016; Saha, et al., 2011). For safe stabilization and reuse of the chromium-

999 containing residue, hexavalent chromium inside should undergo a pre-reduction stage

1000 to its trivalent form with appropriate reducing agents (Fernández Pereira et al., 2007).

1001 The reduced residue with low-valence or metallic chromium as alloying value after

1002 high temperature reduction (> c.a. 1170 °C (Zhang et al., 2000) ) can be reclaimed to

1003 the steelmaking circuit if the material is returned to EAF. In this regard, more
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1004 attentions should be paid to the conversation of chromium-bearing phases in the

1005 residue for better economic values.

1006 Inspection of the current pyrometallurgical processes also shows insufficient

1007 recoveries of nickel and copper in the dust. These two metals have boiling points

1008 higher than the operating temperatures of most metal recovery processes. As a result,

1009 they are concentrated in either the oxide residue or the metallic iron-rich phase.

1010 Similar to chromium, nickel is an alloying element and can be used in steelmaking.

1011 However, copper is generally considered to be a detrimental impurity element in steel.

1012 Thus, it is necessary to recover copper or remove it from the dust. By now, no viable

1013 method has been reported to recover this metal from EAF dust, the oxide residue or

1014 any metallic iron product using these materials as a part of the feed. This problem can

1015 only be resolved by diluting the copper-containing iron with another source of iron

1016 units with a much lower copper content. The separation of copper from iron product

1017 appears to be feasible by cementation combined with suitable treatments (Lindblom et

1018 al., 2002).

1019

1020 7. Conclusions

1021 EAF dust is an important secondary resource that contains a number of metallic

1022 elements. Recycling this dust via appropriate routes such as pyrometallurgical

1023 processes has both remarkable economic and environmental benefits. The authors

1024 reviewed the chemical, physical and thermodynamic characteristics of EAF dust and

1025 the main pyrometallurgical processes for recycling of the dust, from traditional Waelz
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1026 kiln process to unconventional processes such as microwave processing. It is revealed

1027 that the physicochemical features of EAF dust, including relatively high contents of

1028 valued metals (e.g., zinc and iron) and hazardous elements, complex mineralogical

1029 composition, small particle size, low apparent density and moisture content, spherical

1030 morphology, close association of metal-bearing phases and relatively low thermal

1031 stability, favor the use of pyrometallurgical routes for recycling of EAF dust. Most of

1032 the reviewed pyrometallurgical processes are based on carbothermic reduction and

1033 their technical advantages are also supported by low reduction temperatures of oxides

1034 of the valued metals and efficient separation of the metals because of the differences

1035 in their vaporization behaviors. Among the commercial pyrometallurgical processes,

1036 the Waelz kiln process is the main process for recycling of EAF dust but it suffers

1037 from several drawbacks, including waste of iron units, great energy consumption and

1038 high tipping/shipping costs. The RHF direct reduction process is another relatively

1039 mature approach for processing EAF dust with production of high-grade zinc oxide

1040 and DRI. However, it currently only fits the needs of recycling of low-zinc dust.

1041 Several unconventional methods featured by higher processing efficiency and metal

1042 recovery, e.g., microwave processing and solar thermal reduction process, are being

1043 developed for treatment of EAF dust in a more sustainable way. Although many of

1044 them have not commercialized yet mainly due to relatively large initial capital

1045 investment in equipment, they represent future directions of technological innovation

1046 and development in pyrometallurgical recycling of EAF dust. Technically, for further

1047 optimization of treatment of EAF dust, pyrometallurgical recycling of EAF dust has
 ACCEPTED MANUSCRIPT

1048 to confront the challenges due to complex occurrence and association of various

1049 metal-bearing phases in the dust, re-oxidation of the non-ferrous metals after

1050 reduction, and enrichment of hazardous impurities in the generated fume and residue.

1051 To resolve these issues, the detailed exploration of the metal-bearing phases in the

1052 dust based on thermodynamic and kinetics analysis, use of highly-reactive non-

1053 polluting reducing agent like biochar, and treatment of the fume and residue via

1054 additional handling such as pre-reduction or clicking, etc., are necessary. The review

1055 is expected to serve as a useful guide for promoting treatment of EAF dust by

1056 pyrometallurgical processing.

1057

1058 Acknowledgements

1059 This work was partially supported by the National Natural Science Foundation of

1060 China under Grant 51504297, the Innovation-Driven Program of Central South

1061 University under Grant 2016CXS021, the Fundamental Research Funds for the

1062 Central Universities of Central South University under Grant 2016zzts464, and the

1063 Shenghua Lieying Program of Central South University under Grant 502035001.

1064

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1445

1446

1447

1448

1449

1450

1451
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1452

1453

1454

1455 Tables

1456 Number of tables: 5

1457 Table captions:

1458 Table 1 Typical chemical compositions of EAF dust (NA=not analyzed).

1459 Table 2 Typical crystalline phases present in EAF dust.

1460 Table 3 Density and moisture content of EAF dust (NR=not reported).

1461 Table 4 Gibbs free energy expressions of main reactions involved in

1462 pyrometallurgical processing of EAF dust.

1463 Table 5 Pyrometallurgical processes for treatment of EAF dust.

1464

1465

1466

1467

1468

1469

1470

1471

1472

1473
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1474

1475

1476

1477 Figures

1478 Number of figures: 12

1479 Figure captions:

1480 Fig. 1. Particle size distribution of EAF dust (Oustadakis et al., 2010).

1481 Fig. 2. Electron micrograph of EAF dust showing fine dust particles (Simonyan et al.,

1482 2015).

1483 Fig. 3. Scanning electron micrograph and elemental distribution image of EAF dust

1484 (Sofilić et al., 2004).

1485 Fig. 4. TGA profile of EAF dust (Al-Harahsheh et al., 2014).

1486 Fig. 5. Flow chart of Waelz kiln process (Mager et al., 2003).

1487 Fig. 6. Flow chart of RHF process for treatment of EAF dust (Tsutsumi et al., 2010).

1488 Fig. 7. Flow chart of PRIMUS process for treatment of EAF dust (Frieden et al.,

1489 2001).

1490 Fig. 8. Section view of OXYCUP furnace (Wang et al., 2015).

1491 Fig. 9. Flow chart of coke-packed bed process for treatment of EAF dust (Hara et al.,

1492 2000).

1493 Fig. 10. Flow chart of ESRF process for treatment of EAF dust (Nakayama, 2012).

1494 Fig. 11. Flow chart of submerged plasma process for treatment of EAF dust

1495 (Popovici, 2009).

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1496 Fig. 12. Schematic of reaction between ZnFe2O4 and CaCl2 (Guo et al., 2010).

1497

1498
Table 1

Typical chemical compositions of EAF dust (NR=not reported).

Element Low zinc dust (wt.%) Medium zinc dust (wt.%) High zinc dust (wt.%)
(Sofilić et al., 2004) (Sofilić et al., 2004) (Suetens et al., 2015)
Zn 3.75 8.10 27
Fe 48.58 41.08 29
Ca 3.79 4.07 3.1
Na 0.57 0.61 1.5
Pb 1.02 2.07 2.5
Si 1.91 1.91 1.3
K 0.67 0.78 1.2
Mn 5.76 5.18 2.3
S 0.55 0.66 0.6
C 0.38 0.35 3.0
Cl NR NR 3.6
Mg 2.16 2.00 0.4
Al 0.20 0.26 0.4
Ni 0.019 0.023 NR
Cu 0.22 0.27 0.3
Cr 0.22 0.21 0.5
Cd 0.011 0.025 0.1
As <0.01 <0.01 NR
Hg <0.01 <0.01 NR
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Table 2

Typical crystalline phases present in EAF dust.

Element Phases References

Zn Zinc oxide, zinc ferrite, hydrated zinc
chloride
Fe Zinc ferrite, ferric oxide, ferrous-ferric
oxide, ferrous oxide, metallic iron, iron
silicates, iron sulfides, iron sulfates
Ca Calcium oxide, calcium carbonate,
calcium silicates, calcium
aluminosilicates, calcium fluoride,
calcium magnetite
Pb Lead oxide, lead chloride, lead sulfide,
lead sulfate, lead hydroxyl chloride,
lead chloride carbonate
Si Iron silicates, calcium silicates, calcium
aluminosilicates, silicon dioxide
Mg Magnesium oxide, magnesium ferrite
S Iron sulfides, iron sulfates, lead sulfide,
lead sulfate, sulfur
Cl Sodium chloride, potassium chloride,
zinc chloride, calcium chloride, lead
hydroxyl chloride
F Calcium fluoride, sodium fluoride,
potassium fluoride
K Potassium oxide, potassium chloride
Na Sodium oxide, sodium chloride
Mn Manganese oxides, manganese sulfide,
manganese sulfate
Al Aluminum oxide, calcium
aluminosilicates
Ni Nickel oxide, nickel sulfides, nickel
chromite
Cu Copper oxide, copper sulfides
Cr Chromium oxides, chromite, nickel
chromite
Cd Cadmium oxide, cadmium sulfate
da Silva et al., 2008; da Silva Machado et al.,
2006
de Souza et al., 2010; Ma and Garbers-Craig,
2006
Mantovani et al., 2004; Martins et al., 2008
Oustadakis et al., 2010; Ranitović et al., 2014
Oustadakis et al., 2010; Ranitović et al., 2014;
Xia and Pickles, 2000
da Silva et al., 2008; da Silva Machado et al.,
2006
Mantovani et al., 2004; Ranitović et al., 2014
Ma and Garbers-Craig, 2006; Xia and Pickles,
2000
Ma and Garbers-Craig, 2006; Mantovani et al.,
2004
da Silva et al., 2008; Mantovani et al., 2004
Ma and Garbers-Craig, 2006; Mantovani et al.,
2004
da Silva et al., 2008; da Silva Machado et al.,
2006; Ma and Garbers-Craig, 2006
Martins et al., 2008; Ma and Garbers-Craig,
2006; da Silva et al., 2008
Ma and Garbers-Craig, 2006; Mantovani et al.,
2004
de Souza et al., 2010; Martins et al., 2008;
da Silva et al., 2008; de Souza et al., 2010; Ma
and Garbers-Craig, 2006
Xia and Pickles, 2000; Mantovani et al., 2004
 ACCEPTED MANUSCRIPT

Table 3

Density and moisture content of EAF dust (NR=not reported).

EAF Apparent Real Moisture Notes References

Dust density density content
(g cm-3) (g cm-3) (wt.%)
#1 2.53 4.90 0.23 Mixing Nolasc-Sobrinho, et al.,
chamber dust 2003
#2 0.90 4.38 0.62 Baghouse Nolasc-Sobrinho, et al.,
dust 2003
#3 1.01 4.10 NR NR Dai, et al., 2004
#4 NR 4.33 0.17 NR Fedorko, et al., 2012
 Table 4

Gibbs free energy expressions of main reactions involved in pyrometallurgical processing of EAF dust.

No. Reaction ΔGΘ=A+BT Reaction Enthalpy Classification

temperature change
ΔH298Θ
A B (°C) (kJ mol-1)
(J mol-1) (J mol-1K-1)
1 ZnO(s)+C(s)=Zn(g)+CO(g) 362944.64 -295.31 955.88 370.35
2 ZnFe2O4(s) +C(s)=Zn(g)+Fe(s)+CO(g) 855953 -804.09 791.35 872.19
3 PbO(s)+C(s)=Pb(l)+CO(g) 98050.00 -170.28 302.10 113.16
4 CuO(s)+C(s)=Cu(l)+CO(g) 52337.00 -181.52 15.18 57.39
5 MnO(s)+C(s)=Mn(s)+CO(g) 272315.01 -160.21 1426.59 274.40
6 3Fe2O3(s)+C(s)=2Fe3O4(s)+CO(s) 132495.49 -223.46 319.78 132.03
7 Fe3O4(s)+C(s)=3FeO(s)+CO(g) 197349.71 -203.55 696.39 209.38
8 FeO(s)+C(s)=Fe(s)+CO(g) 151872.55 -151.94 726.41 155.31
9 ZnO(s)+Fe=Zn(g)+FeO(s) 211089.01 -143.40 1198.88 215.05 Carbothermic reduction (Waelz kiln,
10 C+CO2(g)=2CO(g) 171143.98 -174.76 706.16 172.47 RHF, PRIMUS, OXYCUP, coke-packed
11 ZnO(s)+CO(g)=Zn(g)+CO2(g) 191800.66 -120.55 1317.90 197.89 bed, Ausmelt, ESRF, Plasmadust, plasma-
12 ZnFe2O4(s) +CO(g)=Zn(g)+Fe(s)+CO2(g) 174271 -108.64 1330.96 182.31 arc, EMPF, submerged plasma, PIZO,
11 PbO(s)+CO(g)=Pb(l)+CO2(g) -62076.00 -14.54 ─ -59.31 flame reactor, iron bath smelting, thermal
12 CuO(s)+CO(g)=Cu(l)+CO2(g) -118807.03 -6.76 ─ -115.08 plasma reduction, microwave processing,
13 MnO2(s)+2C(s)=Mn(s)+CO(g) 294473.41 -355.52 555.14 299.02 solar thermal reduction)
14 3Fe2O3(s)+CO(g)=2Fe3O4(s)+CO2(s) -38648.00 -48.70 ─ -40.40
15 Fe3O4(s)+CO(g)=3FeO(s)+CO2(g) 26206.00 -28.79 637.10 36.91
16 FeO(s)+CO(g)=Fe(s)+CO2(g) -19288.00 22.85 570.96 -17.16
17 CrO3(s)+3C(s)=Cr(s)+3CO(g) 240039.35 -515.58 192.42 246.65
18 CrO3(s)+3CO(g)=Cr(s)+3CO2(g) -273392.59 8.70 31151.28 -270.76
19 FeCr2O4(s)+C(s)=Fe+Cr2O3+CO(g) 222429.50 -167.54 1054.47 220.48
20 CdO(s)+C(s)=Cd(g)+CO(g) 251964.01 -288.92 598.94 260.26
21 CdO(s)+CO(g)=Cd(g)+CO2(g) 80820.00 -114.16 434.80 87.79
22 (ZnO)+[C]= Zn (g)+ CO(g) 308552.64 -271.12 864.92 315.96 Carbothermic reduction (OXYCUP, coke-
23 (PbO)+[C]= Pb(g)+ CO (g) 267096.13 -257.22 765.25 277.21 packed bed, Ausmelt, ESRF, Plasmadust,
24 (FeO)+ [C]=[Fe] +CO(g) 138772.78 -143.70 692.56 145.31 Plasma-arc, EMPF, submerged plasma,
PIZO, fame reactor, iron bath smelting)
25 ZnFe2O4(s)+CaO(s)=Ca2Fe2O5(s)+ZnO(s) -23199.00 -16.89 ─ -27.54 Calcification
26 ZnFe2O4(s)+CaCl2(l)=CaFe2O4(s)+ZnCl2(g) 201882.32 -125.76 1332.15 214.68
27 Fe2O3+3CaCl2(l)=2FeCl3(g)+3CaO(s) 591167.98 -218.30 2434.90 772.85 Halogenation
28 ZnO(s)+CaCl2(l)=ZnCl2(g)+CaO(s) 209953.28 -120.55 1468.48 223.79
Table 5

Pyrometallurgical processes for treatment of EAF dust.

Process Temperature Furnace type Inputs Products Scale Capacity References

(°C) (kt y-1)
Waelz kiln 1150-1200 Rotary kiln Coal, lime/sand,Crude zinc Commercial 40-250 Piret, 2012
natural gas, airoxide and Fe-
slag (waste)
RHF 1250-1300 Rotary hearth Coke, binder, and Crude zinc Commercial 100-300 Nakayama
furnace natural gas oxide and and Taniishi,
DRI/hot 2011
briquetted
iron (HBI)
PRIMUS 1000-1100 Multiple Coal and air Crude zinc Commercial 100 Roth, et al.,
hearth oxide and 2001;
furnace DRI/iron Suetens, et al.,
concentrate 2014
OXYCUP 1500-1600 Cupola Coke, scrap, and Crude zinc Commercial 200 Holtzer, et al.,
bricks (waste + oxide, pig 2015
cement +C) iron, and slag
Coke-packed 1500-1600 Shaft furnace Coke, fluxes, and Crude zinc Commercial 10 Hara, et al.,
bed O2-enriched air oxide, molten 2000;
metal, and Suetens, et al.,
slag 2014
Ausmelt 1250-1300 Top Coal and O2- Crude zinc Commercial 100 Hoang, et al.,
submerged enriched air oxide, and Fe- 2009
lance furnace slag (waste)
ESRF 1300-1500 EAF Binder, air, and Crude zinc Commercial 36 Nakayama,
electricity oxide, pig 2012
iron, and slag
Plasamadust 1400-1600 Shaft furnace Coke, coal, Crude zinc Commercial 10-20 Schoukens et
equipped with fluxes and oxide, molten al., 1993;
 plasma superheated iron, and slag Suetens, et al.,
devices plasma gas 2014
Plasma-arc 1400-1600 Plasma arc Coal, air, and Crude zinc Commercial 5-40 Schoukens et
furnace electricity oxide, molten al., 1993;
iron, and slag Denton, et al.,
2005;
Suetens, et al.,
2014
EMPF 1400-1600 Slag- Coal and air Crude zinc Commercial 40 Schoukens et
resistance oxide, molten al., 1993;
furnace iron, and slag Kennedy, et
al., 2009;
Suetens, et al.,
2014
Submerged 1300-1400 Submerged Coke, Crude zinc Commercial 40-60 Verscheure, et
plasma plasma natural/petroleum oxide and Fe- al., 2007
reactor gas, flux, air, and slag (waste)
electricity
PIZO 1300-1500 Induction Coal, air, Crude zinc Commercial 50 Bratina and
furnace electricity oxide, pig Lenti, 2008
iron and slag
Flame 1600 Flame Natural gas, O2- Crude zinc Commercial 30 Orhan, 2005
reactor Reactor enriched air oxide, molten
metal, and
slag
Thermal 1000-1400 Plasma arc Natural gas/CO, Crude zinc Lab ─ Best and
plasma furnace electricity oxide and Fe- Pickles, 2001;
reduction rich slag for Magdziarz et
steelmaking al., 2015
Microwave 1000-1200 Microwave Coke/coal, air, Crude zinc Lab ─ Sun, et al.,
processing furnace electricity oxide and 2008; Zhou,
DRI et al., 2015
Solar 800-1350 Solar furnace Graphite, silica, Zinc, crude Lab ─ Schaffner et
thermal and sunlight zinc oxide, al., 2003;
reduction and slag Tzouganatos
et al., 2013
Iron bath 1400-1500 ─ Coal/silicon, Crude zinc Lab ─ Chen and
smelting fluxes, and heat oxide, molten Gammal,
metal, and 2000; Grillo,
slag et al., 2014
Calcification 900-1100 ─ CaCO3/lime, O2- Crude zinc Lab ─ Itoh et al.,
enriched air, and oxide and 2008;
heat Ca2Fe2O5 for Chairaksa-
use in blast Fujimoto et
furnace al., 2015
Halogenation 875-1050 ─ PVC and heat ZnCl2 and Lab ─ Guo et al.,
Fe+C pellets 2010