Canadian Metallurgical Quarterly

The Canadian Journal of Metallurgy and Materials Science

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Reduction of Electric Arc Furnace Dust with Solid

Iron Powder

J. R. Donald & C. A. Pickles

To cite this article: J. R. Donald & C. A. Pickles (1996) Reduction of Electric Arc Furnace Dust
with Solid Iron Powder, Canadian Metallurgical Quarterly, 35:3, 255-267, DOI: 10.1179/
cmq.1996.35.3.255

To link to this article: http://dx.doi.org/10.1179/cmq.1996.35.3.255

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 e Pergamon
Canadian Metallurgical Quarterly, Vol. 35, No.3, pp. 255-267, 1996
Published by Elsevier Science Ltd
Printed in Great Britain
0008-4433/96 $15.00+0.00

PH 80008-4433(96)00009-2

REDUCTION OF ELECTRIC ARC FURNACE DUST WITH

SOLID IRON POWDER
J. R. DONALD and C. A. PICKLES
Department of Materials and Metallurgical Engineering, Queen's University, Kingston, Ontario,
Canada K7L 3N6

(Received 31 July 1995; in revised/orm 6 November 1995)

Abstract-Electric arc furnace (EAF) dust contains, on average, about 19mass% zinc and 3 mass% lead.
Due to the presence of this lead, as well as small amounts of cadmium and hexavalent chromium, EAF
dust has been classified as a hazardous waste by various government regulatory agencies. Currently, most
dust treatment processes employ carbon as a reducing agent for the zinc oxide in the EAF dust. The zinc
vapour that is produced can be condensed.
Downloaded by [Monash University Library] at 11:59 02 July 2016

In the present work, the reaction of EAF dust with iron was studied in an argon atmosphere using a
thermogravimetric technique. First, a thermodynamic study was performed using the F*A*C*T com-
putational system. Then, the effects of briquetting pressure, argon flowrate, briquette aspect ratio (lId),
iron particle size, amount of iron added, as well as additions such as lime, sodium chloride and zirconium
oxide on the kinetics of the reduction reaction were investigated. It was found that, initially, the reaction
was chemically controlled with an activation energy of 159kJ Imol. Then, after a product layer had formed
on the outer surface of the briquette, the reaction was controlled by the transport of the zinc vapour away
from the reaction interface. Published by Elsevier Science Ltd

Resume-Les poussieres issues d'un four electrique a arc (EAF) contiennent, en moyenne, environ 19pour-
cent en masse de zinc et 3 pourcent en masse de plomb. En raison de la presence du plomb, ainsi que celIe
de cadmium et de chrome hexavalent en petites quantites, les poussieres issues de l'EAF ont ete classees
dans la categorie des dechets dangereux par les differents organismes gouvernementaux de contrale.
Actuellement, la plupart des procedes de retraitment des poussieres utilise Ie carbone comme agent de
reduction de l'oxyde de zinc contenu dans les poussieres de l'EAF. Le zinc a l'etat gazeux ainsi obtenu peut
etre condense. Le principal probleme rencontre avec ces procedes est la diminution de la stabilite d'un des
produits de la reaction de reduction, Ie monoxyde de carbone, avec un abaissement de la temperature. Ce
phenomene aboutit a l'augmentation du pourcentage de dioxyde de carbone dans les gaz issus de la reaction
lorsqu'ils sont refroidis et une partie du zinc est reoxyde. De plus, Ie cuivre et Ie soufre sont concentres
dans les residus riches en fer et contaminent Ie fer recupere a partir de ces materiaux. Un procede de
remplacement possible consisterait a faire reagir les pousssieres avec du fer solide ou liquide. Dans ce cas,
la vapeur serait principalement composee de zinc, et Ie fer ajoute en tant qu'agent de reduction serait dilue
dans les residus.
Dans Ie present travail, la reaction entre les poussieres de l'EAF et Ie fer a ete etudiee dans une atmosphere
d'argon a l'aide d'une technique thermogravimetrique. Tout d'abord, une etude thermodynamique a ete
realisee en utilisant Ie logicel F*A *C*T. Puis on a examine l'influence de differents facteurs sur la cinetique
de la reaction de reduction: la pression a laquelle les briques ont ete fabriquees, Ie debit du flux d'argon, Ie
ratio de la forme de la brique (lId), la taille des particules de fer, la quantite de fer ajoute, ainsi que
l'addition de produits tels que la chaux ou Ie clorure de sodium. On a trouve qu'initialment la reaction
etait controlee chimiquement avec une energie d'activation de 159 kJ/mol. Ensuite, apres la formation
d'une couche de produit sur la surface exterieure de la brique, la reaction est controlee par Ie transport du
zinc a l'etat gazeux loin de l'interface OU se produit la reaction. La vitesse de reaction suit une loi parabolique
qui a ete ajustee a l'aide des donnees experimentales, et la constante de vitesse de la reaction a ete trouvee
egale a: kp= -3.6241 +O.0033T(K).

INTRODUCTION concurrently. In addition, the dust contains lead, cadmium and

In a typical electric arc furnace (EAF) operation, approximately
1- 2% of the charge is converted into dust [I]. Currently, over
600,000 tons of EAF dust are produced each year in Canada
and the United States [2, 3]. This dust, which can be considered
as a by-product of the electric arc steelmaking process, contains
significant amounts of zinc and iron that can be recovered.
Since the use of galvanized steel continues to increase in the
automotive industry, the amount of zinc in the dust will rise
255
hexavalent chromium, which can be leached into ground water
in concentrations that exceed federal, state or provincial
environmental guidelines. EAF dust has been assigned the haz-
ardous waste number K061 in the United States by the Environ-
mental Protection Agency (EPA) [2], and 143H in Ontario by
the Ministry of the Environment [4].
During the steelmaking process, the temperature in the EAF
generally reaches 1600°C or higher. Under these conditions, vir-
tuallyallofthezinc,leadandcadmiumpresentinthechargeenter
 256 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST

the gas phase. Also, the high temperatures and turbulence in the
EAF cause small amounts of iron, chromium, nickel and manga-
nese to volatilize. As the metal vapours exit the furnace and as
the temperature drops, the fumes oxidize and condense. Physi-
cally and chemically complex microscopic agglomerates form on
condensed nuclei such as fugitive dust particles. These materials
are then collected as particulate matter in the baghouse system.
Essentially, there are three categories of alternative processes:
stabilization of the dust without metal recovery (i.e. disposal in
a hazardous waste landfill site); stabilization of the dust by
combining the dust with another material [5-7]; and treatment
methods that recover the metals while stabilizing the residue
[8-17]. Future liabilities and increasing dumping costs are the
driving forces for more steelmakers to adopt alternative dis-
posal methods to hazardous waste landfilling. Vitrification of
the dust is cheap and easy; however, the long-term stability of
the products are unknown and the metal resources, notably
zinc, contained in the dust are lost. In addition, the material
must undergo rigorous hazardous waste deli sting before land-
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There are currently many different EAF dust treatment
methods. These can be categorized into the following classes:
high temperature metal recovery (HTMR) processes, hydro-
metallurgical processes, plasma processes, and vitrification or
chemical stabilization treatments. Most operators of the high
temperature (including plasma) industrial EAF dust processes
that recover metallic zinc have had problems during the zinc
condensation stage with the re-oxidation of the zinc vapour
with carbon dioxide [14, 23]. The reaction that occurs is as
follows:
Zn(g) + CO2(g)= ZnO(S) + CO(g) (1)
All current pyrometallurgical EAF dust treatments utilize
carbon as the reducing agent, and thus, release carbon dioxide
as an off-gas. One possible alternative to the use of carbon as a
reducing agent would involve metallothermic reduction of the
zinc oxide in the dust with either solid or liquid iron. This could
be accomplished by either pre-reducing the iron oxide in the
dust to metallic iron or by reacting the dust with liquid iron

filling [6]. Current EAF dust treatment methods are energy and according to the following reaction:
cost intensive, require risky transportation to the processing
site, and while the zinc, lead and cadmium are recovered, the ZnO(S) + Fe(sor I) = Zn(g) + FeO(sor I) (2)
iron is usually discarded.
With metallic iron as a reducing agent, the gas volumes are
Approxilnately S0-800/0 of the zinc contained in the dust is
reduced and since there is no carbon dioxide present it may be
in the form of zinc oxide (ZnO). The remainder occurs as a zinc
easier to condense the zinc in metallic form. Also, the zinc or
ferrite (ZnO . Fe203) spinel. Small amounts of zinc may also be
zinc oxide purity may be higher. In addition, the reacted iron
present in llletallic form, or as sulphides, silicates, or aluminates.
can be recovered by recycling the residue in the iron or steel-
The majority of the iron is found as hematite (Fe203), or ferrite
making process.
spinels, but some metallic iron may also be detected. Lead
In Japan, the iron reduction distillation process has been
mainly occurs as an oxide but some lead sulphate and lead
developed by researchers at Tohoku University [24]. The pro-
chloride may also be present. Lead oxide, like zinc oxide, tends
cess consists of two reduction stages. The first stage involves
to be present in small discrete particles, or as smaller regions
the preferential reduction of the iron oxide in the dust by
within a larger particle. The lead oxide is not found within any
employing a CO2/CO gas ratio of 0.1 at a temperature of 700-
of the spinels. The distribution of cadmium within the dust is
800aC [25]. In the second reduction stage at a higher tempera-
not well understood, but it would be expected that it would
ture, the zinc oxide in the dust was easily reduced and volatilized
behave in a similar manner to zinc [5].
by the metallic iron in a vacuum of IPa. The zinc was distilled
Previous researchers have used reflected light microscopy
rapidly; for example, all of the zinc was removed within 20 min
(RLS), scanning electron microscopy-energy dispersive spec-
at 1100cC. The behaviour of the minor elements in the dust was
troscopy (SEM-EDS), and cathodoluminescence microscopy
found to be related to the chlorine content. During the first
(CLM) to examine the EAF dust [18, 19]. Their results indicate
reduction step, all of the cadmium and most of the lead were
that the predominant mineralogical phases are the iron spinels,
vaporized in the form of chlorides. The copper was concentrated
magnetite (FeO· Fe203), zinc ferrite (ZnO· Fe203) andjacobsite
in the metallic iron. The minor elements were not affected in
(MnO . Fe203), solid solutions of those three spinels, zincite
the second reduction stage [2S].
(ZnO) and fayalite [(FeO)2 . Si02]. In the samples that contained
In the present work, the reaction of EAF dust with solid
a high zinc content the prevalent phases were found to be zinc
electrolytic iron powder in an inert atmosphere was studied.
oxide and zinc ferrite.
First, a thermodynamic analysis was performed using the
The EAF dust particles are, generally, less than 10 pm in size,
F* A *C*T system. Then, the effects of briquette size, tempera-
while the majority of the particles are less than 1 pm. Some of
ture, ratio of reactants, size of iron particles, argon flowrate,
the particles are less than one-tenth of a micron and the fine
briquetting pressure and lime, zirconium oxide and sodium
particles readily agglomerate. Physical separation methods
chloride additions on the reduction rate were investigated using
exhibit poor recoveries because of the extremely small particle
a thermogravimetric technique. A reaction mechanism is pro-
sizes [S]. The specific area of the dust has been estimated to be
posed based on the experimental observations.
2.S-4.0 m2/g by the BET method [20], and 0.7 m2/g using the
Blaine air permeability apparatus [21]. The density of the dust
has been found to be in the range 1.1-2.5 g/cm3 [22]. The density
of the dust is strongly dependent on the moisture content, which THERMODYNAMIC CONSIDERATIONS
can vary from approximately 0 to 500/0. In part, the moisture
content depends on the lime concentration in the dust [8]. Due The important reactions and the standard free energy changes
to the relatively low density values, the dust is too voluminous involved in the reduction of the zinc oxide in EAF dust with
for economical disposal. iron powder, are described in Table 1.
 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST 257

Table 1. The reactions of the components of electric arc furnace (EAF) dust with iron and the standard
free energy changes

Reaction no. Reaction I1GO (JImol)

3 Fe203(s) + Fe(s) = 3 FeO(s) 19676.9-31.49 T (K)

4 Fe304(s) + Fe(s) = 4 FeO(s) 29419.9-31.11 T
5 ZnO(s) + Fe(s) = Zn(g) + FeO(s) 204066.8-138.33 T
6 ZnO . Fe203(spo)+ 2 Fe(s) = Zn(g) + FeO(s) 229735.6-197.9 T
7 ZnO(s) + 3 Fe(s) + 2 CaO(s) = 3 Zn(g) + Fe(s) + 187307.9-126.2 T
(2CaO)· Fe203(spo)
8 ZnO . Fe203(spo) + Fe(s) + 2 CaO(s) = Zn(g) + 178808.4 - 162.0 T
FeO(s) + (CaO)2' Fe203(spo)
9 PbO(s) + Fe(s) = Pb0(1) + FeO(s) - 51178.0 - 29.74 T
10 CdO(s) + Fe(s) = Cd(g) + FeO(s) 89863.1 - 128.03 T

The free energy change of the reactions can be described by EXPERIMENT AL

the van't Hoff equation:
I!J.G = I!J.GO + RTln Q The raw materials employed in the reduction of the EAF
(11)
dust with iron were EAF dust, electrolytic iron powder, iron
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where R is the Universal gas constant, Tis the temperature and
Q is the effective reaction constant (activity quotient at a given
time). In an open system, the partial pressure of the gaseous
product will be much lower than unity. Thus, lower partial
pressures of zinc, cadmium or lead will lower the free energy
change of the respective reactions. The facility for the analysis
of chemical thermodynamics (F* A *C*T) [26] was employed to
calculate the free energy changes of reactions (5) and (6) at
various zinc vapour pressures, and the results are presented in
Fig. 1. In a closed system (i.e. p(Zn) = 1 atm.), the free energy
change of reaction (5) is zero at 1202°C, and thus, above this
temperature the reduction of zinc oxide with iron would be
expected. At zinc pressures of 0.01 and 0.0001 atmospheres, the
temperatures at which the free energy changes are zero are
approximately 800 and 650°C, respectively. In the case of the
pure zinc ferrite reduction with iron [reaction (6)], the reaction
would be expected to occur above 800°C in a closed system.
However, at lower zinc pressures of 0.01 and 0.0001 atmo-
spheres, the free energy change is zero at about 650 and 500°C.
Also, lime additions promote the formation of calcium ferrite,
which will lower the activity of the iron oxide, and thus decrease
the free energy change of the reactions.
filings, calcium oxide, sodium chloride and zirconium oxide.
The EAF dust was obtained from CO-STEEL LASCO in
Whitby, Ontario. The elemental chemical composition of the
dust is shown in Table 2. The major elements in the dust are
iron and zinc. Also, there are relatively high concentrations of
the hazardous elements, such as lead and cadmium. In addition,
the dust contains significant quantities of alkalis and halides.
The concentrations of some of the main compounds in the dust
are shown in Table 3. The zinc occurs in the dust as zinc metal,
zinc oxide and zinc ferrite. The iron occurs as pure ferric oxide,
as well as part of solid solutions involving various oxides.
All of the other chemical reagents used in the experiments
were analytical reagent grade and were purchased from B.D.H.
Chemical Company and were all -200 mesh (Tyler) in size,
except where the iron particle size was varied.
An X-ray diffraction pattern of the unreacted EAF dust is
shown in Fig. 2. The major peaks in the pattern indicate that
the EAF dust contains significant quantities of zinc oxide, zinc
ferrite, sodium chloride, potassium chloride and lime.
The reactants were mechanically mixed together and were
formed into cylindrical briquettes by compacting the powder in
a 13.0mm internal diameter (i.d.) cylindrical mould under a
standard load of 425 kg.cm -2 for 30 s. This alloy steel floating

50000 ./'

P = 1 atm. Table 2. Elemental composition of Co-Steel Lasco EAF dust

o p Z~ 0.01
Zn
\~a:~.
-1 "
Element

Iron (Fe)
Concentration (mass%

16.55 ± 1.35%
or ppm)

/>- -- .
'0 -50000 P = 0.0001 atm. . Zinc (Zn) 24.8± 1.4%
Cadmium (Cd) 714±9 ppm
Lead (Pb) 3.22±0.07%
Chromium (Cr) 1340 ppm
~ -100000 Zn .,\""'""""", .
Calcium (Ca) 11.5±0.7%
Magnesium (Mg) 0.75%
-150000 Manganese (Mn) 1.55%
- Reaction (5) Silicon (Si) 1.3%
Carbon (C) 0.94%
-200000 L....--_-_. _R_e_ac....Lt_io_n_(_6_) --L --'-- __ ~ Sodium (Na) 4.75%
600 800 1000 1200 1400 Potassium (K) 1.9%
Chlorine (CI) 4.05%
Temperature (Oc)
Fluorine (F) 2550 ppm
Fig. 1. The effect of partial pressure on the free energy change of Sulphur (S) 4000 ppm
reactions (5) and (6).
 258 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST

Table 3. Estimated concentrations of some common compounds in

Transducer
Co-Steel Lasco EAF dust

Compound/spinel massO/o Hot box--......

Zinc metal 6.45%

Zinc oxide (ZnO) 21.4% Ar
Zinc ferrite (ZnO . Fe203) 25.8%
Hematite (Fe203) 2%
Calcium oxide (CaO) 15.6%
Lead oxide (PbO) 3.4%
Silica (Si02) 3.4% ,......Flowmeter
Sample
Manganese oxide (MnO) 2.2%
Magnesia (MgO) 1.4% Furnace "----
Alumina (AI203) 0.7%
Chromium oxide (Cr203) 0.2%
Sodium chloride (NaCl) 6.6%
Potassium chloride (KCl) 3.6%

Fig. 3. Schematic diagram of the experimental apparatus.

mould, with the movable plungers at both ends, was used to

Downloaded by [Monash University Library] at 11:59 02 July 2016

produce uniform briquettes. In each of the experiments the
aspect ratio (lId) of the briquettes was greater than one, except
where the aspect ratio was varied. The standard length of the
briquette was 18 mm. The size, density, porosity, surface area
and texture of the briquettes were easily reproduced. The
stoichiometric amount of iron for complete removal of zinc was
added unless otherwise specified. Using the estimates of the
EAF dust compositions shown in Tables 2 and 3, the stoi-
chiometric amount of iron was determined to be 18 mass% of
the total briquette mass.
Figure ::; is a schematic diagram of the thermogravimetric
apparatus. Commercial purity argon was used to provide an
inert atmosphere in the experiments. Prior to the experiment,
the furnace was flushed with argon for 30 min to ensure that no
oxygen was present and also to allow the equilibration of the
temperature in the hot zone of the furnace.
The furnace consisted of a 25 mm (i.d.) Inconel tube, which
was heated by two Nichrome resistance elements. This created
a uniform 80 mm constant temperature zone. The temperature
of this hot zone was maintained constant by a highly accurate
solid-state CAL 7000 temperature controller connected to a K-
type (chromel-alumel) thermocouple located in the constant
temperature zone on the outside of the Inconel tube. The sample
temperature was measured immediately before and after each
experiment by placing a K-type thermocouple directly into the
hot zone. The temperature in the hot zone was maintained
within ± 5°C. The sample was suspended in a pre-oxidized
chromel strip basket, which was supported by a chromel wire.
A Stratham transducer, which was situated directly above
the furnace, provided a continuous measurement of the sample
mass. The chromel wire, which supported the briquette, was
connected to the transducer by a fine thread that damped out
any small vibrations in the supporting wires. The transducer
was housed in a hot box to keep the temperature fluctuations
and air disturbances to a minimum. The deflection of the trans-
ducer, due to the mass change, was converted to a signal which
was recorded on an X- Y strip chart recorder. The change in
mass during the reduction process was therefore known at every
instant. Some volatile materials that are contained in the EAF
dust would be expected to leave the briquette with the zinc
vapour. In order to verify the reproducibility of the reduction
experiments, two control samples were reduced under identical
conditions. The maximum variation in the percentage reduction
between the two curves was 4.2% for the EAF dust experiments.

I-ZnO
2-ZnOFe203
3-Halides
-NaCI
-KCI
4-CaO

70 60 50 40 30 20 10
28
Fig. 2. X-ray diffraction (XRD) pattern of the unreacted EAF dust.
 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST 259

Table 4. Mass of various elements in a briquette of EAF dust before and after heating. Also included is the
composition of the fume. The total mass loss of the briquette was 0.54 g or 10.9%

Element Zn Pb C S CI K Other Total

Original mass in briquette 1.21g 0.151g 0.046g 0.02g 0.2g 0.093g 3.431g 5g
After heating 1.20g 0.091g 0.022g 0.02g 0.028g 0.007g 3.243g 4.46g
Mass loss O.Olg 0.06g 0.024g Og 0.172g 0.086g 0.188g 0.54g
Mass % of Fume 1.85% 11.1 % 4.44% 0% 31.9% 15.9% 34.8% 100%

This relatively high variation was due to the inconsistent nature
of the EAF dust composition. The amount and form of zinc
can vary throughout the dust, and the reduction rate can be
affected by various other elements and compounds in the dust
which are present in very small concentrations.
A JOEL JSM-840 scanning electron microscope (SEM)
equipped with a Tracor Northern 5500 energy dispersive X-ray
spectrometer (EDS) was utilized to obtain micrographs and to
analyze the spent briquettes for a variety of elements. The
Downloaded by [Monash University Library] at 11:59 02 July 2016
of the EAF dust experiments such that a good estimate of the
percentage zinc removal could be made. Also, it was assumed,
based on this evidence, that the sodium chloride additions
would be removed from the briquettes. Thus, in the experiments
in which sodium chloride was added, this additional sodium
chloride mass loss was taken into account when the percentage
zinc removal was calculated. In addition, the samples that were
reacted at various temperatures for 6 h were analyzed for zinc
by the induction coupled plasma (ICP) method. The percentage

phases present in the spent briquettes were determined by the
analysis of the X-ray diffraction patterns generated on a Rigaku
CN2005 Miniflex X-ray diffractometer, which employed Cu-
Ka radiation. Unreacted EAF dust and selected spent briquettes
were analyzed for zinc, lead, chromium, cadmium, potassium,
sodium, magnesium, silicon, manganese, calcium and copper
by the induction coupled plasma (ICP) method. Chlorine ana-
lysis was performed by wet chemistry, and the carbon and the
sulphur contents were determined by the LECO method.
RESULTS AND DISCUSSION
To determine the mass loss of the briquette that could not be
attributed to the removal of zinc, a briquette of the EAF dust
with no added iron was heated at 950°C for a period of 6 h. The
mass loss was recorded, and the sample was analyzed for the
following elements: zinc, lead, potassium, chlorine, sulphur and
carbon. The results from this experiment are shown in Table 4.
Negligible amounts of zinc, carbon and sulphur were removed
from the briquette. Almost all of the potassium and chlorine
were removed from the EAF dust, as well as a significant por-
tion of the lead. In total these elements accounted for 65% of
the mass loss of the EAF dust briquette. The remaining mass
would be expected to be composed of water, cadmium, fluorine
and sodium. These results were utilized to adjust the mass loss
zinc removal results calculated in this manner were in good
agreement with those calculated from the mass loss of the
sample. In each of the experiments, a small amount of material
condensed on the basket and the chromel wires. This amount
was less than 0.1 g per sample.
Table 5 shows the percentage reduction of the zinc oxide in
the EAF dust briquettes containing stoichiometric iron at vari-
ous argon flowrates. The results are essentially identical, and
thus there is no effect of gas flowrate (in the range 0.0012-
0.0040m3• min-I) on the reaction kinetics. In subsequent
experiments a standard gas flowrate of 0.0021 m3. min-I was
employed. This flowrate was above the critical value necessary
to ensure that the reaction rate was not dependent on the rate
of zinc vapour removal from the reaction zone.
The effect of briquetting pressure on the percentage zinc
removal from the EAF dust at a reaction temperature of 950°C
is shown in Table 5. There appears to be a small effect of
briquetting pressure between 140 and 700 kgjcm2• The samples
that were briquetted at higher pressures have slightly lower
percentage zinc removal values than those briquetted at lower
pressures. At lower briquette pressures, the zinc vapour in the
interior of the briquette could escape more easily, and thus, the
reaction proceeded more rapidly.
The effect of the length of the briquette on the percentage
zinc removal is shown in Fig. 4. The samples were reacted at a
temperature of 950°C. The lengths of the briquettes were varied

Table 5. Effect of argon flowrate and briquette pressure on the percent zinc removal for the reaction
of EAF dust with iron

Percent reduction at various times

Argon flowrate m3/min Temperature 20 min 40 min 60 min 100min

cae)
0.0012 940 18.9 31.9 41.7 53.3
0.0031 940 19.4 31.9 41.7 54.3
0.0040 940 19.4 31.5 40.8 52.9
Briquette pressure kg/cm2 1h 2h 4h 6h
140 950 49.6 64.0 74.6 78.86
425 950 46.3 62.2 72.8 77.5
700 950 45.9 60.4 71.7 76.4
 260 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST
100 100

90
v_v 90

80 v--_.
v~"'~~:=-
80
~.------
.-.=--.
.-.-- 0------'
70 ~;~i 70
g
I' /0
:/ /0--£> __
g
6
~i~
'@
60 i~ ~> 60 £>~

~
0
>
SCIJ
50

40
/ v
•
.•.
1/d=O.56
1/d=1.4-std
1/d=1.8
E
c:;
0:::
0
50

40
.;/ o

~
~/

,,-/
,------'
<>

N
s:: o 1/d=2 ()

>:: :; /' 0------

.30 N
30 ~ ,------" T=1050°C

20 20 ~"~:-:>/o,,:::::.----
:
0
T=1000°C
T=950°C
T=900°C
10 10 / T T=850cC
Temperature = 950°C y ~ T=800cC
.3 0
2 4 5 0 .3 5 8
Time (hrs) Time (hrs)
Fig. 4. The effect of briquette size on the percentage zinc removal from Fig. 6. The effect of time on the percentage zinc remoyal from EAF
EAF dust. The reaction temperature was 950cC. dust at various reaction temperatures.
Downloaded by [Monash University Library] at 11:59 02 July 2016

in the range 7-22 mm. Initially the percentage zinc removal was
linear with time, then the reaction rate became non-linear. The
linear region is more clearly presented in Fig. 5, which shows
the data for the initial hour of the reduction of the standard
briquette at 950°C. The samples which had a length greater
than the diameter (i.e. aspect ratio (1/d) > 1) showed similar
zinc removals. However, the briquette which had an aspect
ratio of 0.55 (length of 7 mm), had an accelerated rate of reac-
tion after the first two hours. In this case, the volatilized zinc
gas in the central regions of the briquette diffused out of the
ends of the cylindrical briquette, since this represented a shorter
diffusion distance for the zinc vapour than through the sides.
For the briquettes with aspect ratios (I/d) greater than one, the
shortest distance for the zinc gas in the centre of the briquette,
was through the sides. Thus, the reaction of the shorter
briquette proceeded faster and the percentage reduction at a
given time was higher than that observed for the longer briquet-
tes. These results indicate that the diffusion of the zinc gas has
a major effect on the kinetics of the reduction of the zinc oxide
in the EAF dust.
The effect of temperature on the percentage removal of zinc
is presented in Fig. 6. At a relatively low temperature of 800°C,
about 40% of the zinc was removed from the dust after a
reaction time of 6 h. At intermediate temperatures, the effect of
temperature was dramatic. At 850 and 900:::C the zinc removals
were about 50 and 780/0, respectively. It would be expected that
the reduction rate would increase with increasing temperature
throughout the entire period of the experiment. However, the
briquette reacted at 1000GC had a zinc removal rate similar
to the briquette reacted at 950GC after 3 h. In both of these
experiments, the zinc removal was about 80% after 6 h. At
1050°C, the percentage zinc removal was only 70% after 6 h.
This effect can be attributed to the sintering of the briquette.
When sintering occurred, the zinc vapour could not diffuse to
the outer surface of the briquette, and thus the partial pressure
of zinc within the briquette increased rapidly.
The volume decreases of the briquettes, reacted for a 6 h
period, over the temperature range 800-1050GC, are shown in
Fig. 7. The briquette volumes decreased with increasing reaction
temperature, which indicates a progressively higher degree of
sintering. The briquette that reacted at 800GC did not show a
significant volume decrease, while the briquette that was
reduced at 1050°C had a volume decrease of over 450/0. These
results indicate that the reaction is very temperature sensitive

60 50

50
/.
40
•

/
• g
g 40
CJ
III
30
ta> (OJ

~
ll>
0 30 ()

E
~
IV
CJ
Q •

/
CJ
20
>:: E
:::J
N 20
0
>
10
10 •
0
0 10 20 30 40 50 60 70
0
800
/ 900 1000 1100
Time (mins) Temperature (OC)

Fig. 5. The effect of time on the percentage zinc removal from EAF Fig. 7. The effect of temperature on the volume decrease of briquettes
dust. The reaction temperature was 950°C. containing EAF dust and iron. The briquettes were reacted for 6 h.
 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST 261
-6

100
EA = 159.1kJ/mol

80
g
-8
• ~> 60
0

~ S
.s
Q)

ec: 40
s::
N
20
-10
0
40 1200
1100
30
~o 1000
".I) <1 20 900 . ~Cl
-12 '-- ----J'--- ---'- ---J

(/(/~(/ 800 :c'O-\.v:~,e

0.7 0.8 0.9 1.0
~ ,\e~?e
1000/T (K)
Fig. 10. The effect of temperature on the zinc removal from EAF dust
Fig. 8. Arrhenius plot of In k versus 1000/T.
at various iron additions. The reaction time was 1 h.
Downloaded by [Monash University Library] at 11:59 02 July 2016

and that the zinc vapour removal from the interior of the
briquette plays an important role in the reduction rate.
An Arrhenius plot (In k vs 100011) obtained from the exper-
imental data is presented in Fig. 8. The rate constant, k, was
calculated in units of percentage reduction per second. The
activation energy of the initial process was calculated to be
159.1 kllmol. This value is less than the values obtained for
the pure zinc oxide (230 kl jmol) [27] and the pure zinc ferrite
(178.1 kllmol) [28]. This may be due to the presence of lime,
alkalis and alkaline earth materials in the EAF dust, which
accelerate the reduction process. In all cases, the activation
energy is relatively high and, thus, it would be expected that
initially the reaction is chemically controlled.
The effect of the amount of iron added to the EAF dust
before reduction is shown in Fig. 9. The samples were reacted
at a temperature of 950°C. The stoichiometric iron addition was
calculated to be 18mass% of the briquette using the estimates of
the EAF dust composition given in Tables 2 and 3, and the
reactions involved, as shown in eqns (3)-(10) (Table 1). The
percentage zinc removal increased with increasing iron content
100
v 10% Fe Addilfion o~
90 • 18% ~T
30% ~
80
48% /:~.
70
until the iron addition reached about 30% of the briquette
mass. Increasing iron additions resulted in an increase in the
reaction surface area. A small portion of the zinc in the dust was
present as metallic zinc, which would be expected to vaporize at
the reaction temperatures. Also, there is some metallic iron in
the dust, which would participate in the reaction. In addition,
about 1mass% of the dust is carbon, which would preferentially
reduce some of the iron oxides to iron. Iron additions of 10 and
18% of the briquette mass resulted in 50 and 80% zinc removals,
respectively, after 4 h. The briquettes which contained 30 and
48 mass % iron were essentially 100% reduced after 4 h. After a
period of 2 h the rate of zinc removal was similar for all of the
briquettes with iron contents above the stoichiometric amount
(18 mass%). An increase in the surface area of the reactants will
increase the rate of the reaction during the period that the
reaction was chemically controlled, in this case, the initial
period.
The effect of temperature on the percentage zinc removal
from the EAF dust at various iron additions after a reaction
time of 1h is presented in Fig. 10. The percentage zinc removal
increased with increasing iron additions and temperatures up
to 1000°C. With an iron addition of 40 mass % and a reaction
temperature of 1OOO°C,87% of the zinc was removed from the
EAF dust during the initial hour of the experiment. At a reac-
tion temperature of 1050°C, the zinc removal was 23% with an
addition of 18mass% iron. The zinc removal increased to 77%
with an iron addition of 40mass%. These effects occur for two
•
reasons. First, an increase in the amount of iron increases the

:/
g
60 surface area of the reaction interface, which increases the rate
a;
>
0

SClJ
50
v.----- .--. of the reaction. Secondly, increased iron additions reduce the
amount of sintering.
~
N
s::
40
v
/ The effect of temperature on the percentage zinc removal
30
from the EAF dust at various iron additions after a reaction
20 time of 4 h is shown in Fig. I I. The percentage zinc removal
10
increases with both the amount of iron added and the tem-
Temperalure=950°C
perature up to 1000°C. At 900°C and an iron addition of
0
0 2 3 4 5 18mass %, the zinc removal was 650/0,while at 1000°C, and an
Time (hrs)
iron addition of 40 mass % the zinc removal increased to 97%.
At a reaction temperature of 1050°C, the zinc removal was 54
Fig. 9. The effect of reaction time on the percentage reduction of the
briquettesat iron additionsof 10-40%. Thereductiontemperaturewas and 90% at iron additions of 18 and 40mass%, respectively.
950°C. These results indicate that reaction surface area and the effect
 262 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST

100 /~ ___ [J

j"/
100

so
90

80
.tj/ /.----- .~:==.-. .-Y

g
70 a
f" "'/
· Control

fll,/ ::~;.~:~
60 v 5% CaO
d
::-
0 50
a
Q)

0:: • 20% CaO

40
c
N
30

20

1200 10
1100 Temperature = 9500

1000
900 0
0 3 4 5 6
800
<tet1Wera\,ure ~oc)
Time (hrs)
Fig. 11. The effect of temperature on the zinc removal front EAF dust Fig. 13. The effect of lime (CaO) additions on the percentage zinc
at various iron additions. The reaction time was 4 h. removal from the EAF dust. The reduction temperature was 950:C.
Downloaded by [Monash University Library] at 11:59 02 July 2016

of sintering play an important role in the reduction of EAF
dust.
The effect of iron particle size on the removal of the zinc from
the EAF dust briquettes is shown in Fig. 12. The samples
were reacted at a temperature of 950oe. The rate of reduction
increased with decreasing iron particle size. This would be
expected since a smaller iron particle size would result in higher
reaction surface area. The reaction rate increased with the smal-
ler sized iron particles for the first 2 h, while after this period,
there was little difference between the curves.
The effect of lime additions on the percentage zinc removal
from the EAF dust is shown in Fig. 13. The reaction tem-
perature was 950oe. Lime additions in the range 10-200/0
increased the rate of zinc removal from the dust. A lime addition
of 5°1o had little effect on the reaction. The sample that con-
tained no added lime had a zinc removal of about 80°/0, while
the sample with 200/0 lime was 100% reduced after 3 h. A lime
addition of 15°/0 resulted in 100% zinc removal after a reaction
time of 5 h. As discussed previously, lime additions lower the
free energy of the reaction by forming a calcium ferrite solid
solution. Also, Fe3+ was formed in the products, as opposed to
Fe2+, and thus, the iron was more efficiently utilized. The reac-
tion rate was only significantly affected by lime additions in the
first two hours of the experiment. After this period, the reaction
rates were independent of lime additions.
The EAF dust contains about 16 massolo lime, which has been
previously shown to promote the reduction of the zinc oxide
and the zinc ferrite with iron [27, 28]. However, a significant
portion of the lime in the dust may be in the form of a calcium
ferrite spinel, and this lime does not participate in the reactions.
Also, the lime added to the EAF dust may preferentially form
calcium ferrites with the iron oxides present, before the iron
oxides are reduced by the added iron. Thus, small lime
additions, such as 5°1o, had no effect on the reaction rate.
Figure 14 shows the effect of temperature on the percentage
of zinc removed from the EAF dust with various lime additions
after a reaction time of 1 h. The percentage zinc removal increased
with both increasing temperature up to 1000ce and increasing
lime content. The effect of the lime additions was more pro-
nounced at the higher temperatures. This was particularly dra-
matic at a reaction temperature of 1050ce. With no lime
addition and a temperature of 1050ce, the zinc removal was

100 ,...----r----r----,-----r-----,
• Control (-200 mesh)
90 f-- •••. +100 -150 mesh
100
v +35 -48 mesh
SO
80
70
g E
60 ~ 60
ro::- a
0
50 8
a
Q)
~ 40
0::
40 c
N
c 20
N
30
a
20 1200
15
1100
10 10
Temperature = 950°C 1000
O.._--....l...---...L...---...L...---...L...-------' 900 ~Cl
e
o 2 3 4 5 800 e't'3-'\,
\}'t

'\.e'{\\~
Time (hrs)

Fig. 12. The effect of iron particle size on the percentage zinc removal Fig. 14. The effect of temperature on the zinc removal from EAF dust
from the EAF dust. The reaction temperature was 950°C. at various lime additions. The reaction time was 1 h.
 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST 263

Metal oxide systems

Crystalline phases
Notation Oxide formula
167P Cristobalite }
Tridymite Si02
Pseudowollastonite CaO.Si02
Rankinite 3CaO.2Si02
Lime CaO
Hematite Fe203
Magnetite FeO.Fe203

Temperatures up to approximately 1550°C

are on the geophysical laboratory
scale; those above 1550°C are on the
1948 international scale.
Downloaded by [Monash University Library] at 11:59 02 July 2016

CaO 1438° CaFe204 1216° 1205°1226°1358°

-2570° 2CaO.Fe203 CaO.Fe203 CaO·2Fe203
1449°
Fig. 15. The CaO-FezOrSiOz phase diagram.

35% after 1h, however, under the same conditions and a lime
addition of 15mass%, the zinc removal was 92%. This increase
in zinc removal is due to two factors. First, the lime alters the
reaction such that calcium ferrite is produced, and thus, the
iron oxide product activity is lowered and the iron is more
efficiently utilized. Secondly, lime additions will increase the
temperature at which the briquette sinters. Lime, which has
a melting temperature of 2572°C, will increase the liquidus
temperature of the dust. The CaO'-Fe20'3-Si02 phase diagram
is presented in Fig. 15. EAF dust can be considered to lie in the
shaded region, where there are several calcium ferrite spinel
and solid solutions. The liquidus temperatures in these areas
increase as the amount of lime in the solution increases. At
1050°C, with a lime addition of 15mass %, the volume decrease
of the briquette was 35% compared to a 47% volume decrease
in the sample without lime. Thus, zinc vapour diffused more
readily when sintering was inhibited by the lime additions.
The effect of temperature on the percentage zinc removal
from EAF dust for various lime additions after a reaction time
of 4 h is presented in Fig. 16. The percentage zinc removal
again increased with increasing temperature and lime additions.
However, the effect was not nearly as pronounced as that
observed for a reaction time of 1h. At lime additions of
15mass %, the zinc removal was 78 °10 at 900°C and 91 °10 at
1050°C. With no lime additions, the zinc removals were 65 and
54°10 for reaction temperatures of900 and 1050°C, respectively.
These results indicated that the removal of zinc from the EAF
dust briquettes was extremely sensitive to briquette sintering,
which restricted the escape of the zinc vapour from the reaction
zone and this resulted in an increased partial pressure of zinc
in the briquette.
The effect of zirconium oxide additions on the percentage
zinc removal, at various reaction temperatures, is shown in Fig.
17. The F*A*C*T database predicts that zinc oxide, zinc ferrite,
ferrous oxide and ferric oxide will not react with zirconium
oxide at the reaction temperatures. Thus, this additive, which
has a relatively high melting temperature of 2700°C, does not
affect the thermodynamics of the reaction, but will decrease the
amount of sintering. The 5 mass % zirconium oxide addition
substantially increased the rate of the reaction. At a temperature
of 1050°C, the sample without zirconium oxide added had a
zinc removal of about 60%, after a reaction time of 6 h. The
 264 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST

100

90

80

70
g 60
c:;; • Control
~ "C' 3% NaCI
0
50
EC> y 5% NaCI
0:::
40
s::
N
30

1200 20
15
1100
10 10
1000 Temperature = 950°C
~o 5 IO~
O~-_..I.- __ ..I.-_---'-----'-------'
"'1(1, 900 v~e "-
Q'(;lQ' 0 800 e~'3-\; o 2 3 5
4;; ,\e~~
Time (hrs)
Fig. 16. The effect of temperature on the zinc removal from EAF dust Fig. 18. The effect of sodium chloride additions on the percentage zinc
at various lime additions. The reaction time was 4 h. removal from EAF dust The reaction temperature was 950~C.
Downloaded by [Monash University Library] at 11:59 02 July 2016

sample contaInIng the zirconium oxide additive had a zinc lization of the pellet. It appears that, in the presence of alkalis,
removal of almost 90%, after a reaction time of3 h. The volume the cracking of the pellet was due to the growth of high strength
decrease of the briquette reacted at 1050°C with zirconium iron whiskers. In the present investigation, this phenomenon
oxide added was 350/0, much less than the volume decrease of could increase the porosity of the product layer, and thus,
47%, without the additive. These results confirm that briquette increase the reaction rate.
sintering is a major factor in the kinetics of zinc removal from The percentage lead removal as a function of temperature is
the EAF dust. presented in Fig. 19. The lead removal increased with tem-
The effect of sodium chloride additions on the percentage perature up to 950°C, where the removal was 99.5%. At higher
zinc removal from the EAF dust is shown in Fig. 18. The temperatures the percentage lead removal decreased due to
samples were reacted at a temperature of 950°C. The sodium sintering of the briquette. Also, the reduction oflead oxide with
chloride additions had little effect on the reaction rate. In the iron is exothermic, as shown in eqn (9), and thus, some localized
original EAF dust, there are significant quantities of sodium heat from the reduction may assist in the vaporization of the
chloride (6.6%) and potassium chloride (3.6%) present. The lead. Also, lead oxide has a relatively large vapour pressure of
results indicate that the amount of sodium chloride in the EAF 3.27 x 10-5 atm. at 950°C compared to 1.5 x 10-3 atm. for
dust is sufficient to catalyze the reaction, and further additions pure lead. Thus, a portion of the lead oxide in the dust may
have little effect. In the reduction of pure zinc oxide with iron have vaporized.
[27], it was found that additions over 1 mass% sodium chloride All of the cadmium was removed over the entire temperature
did not affect the reaction rate. Sodium chloride additions up range tested. This result was expected considering the low tem-
to 3 mass% promoted the reaction between pure zinc ferrite perature at which reaction (l0) occurs and the relatively low
and iron [28]. Previous investigations [29-31] have shown that boiling point of cadmium (765 C) [32]. C

during the reduction of sintered hematite, small concentrations X-ray diffraction patterns of briquettes containing EAF dust
of sodium promote cracking and swelling during the metal- with an 18 mass% iron addition, reacted for a period of I, 3

100 100

90 90

g
80

70

60
1/---
I.
9~~ ----

...____<7
g
80

70

co~ I ~"7 c:;;

60
0
50
/"7 ~
EC> "V
0
50
E
0:::
40 / C>
0:::

N
CJ
s::
30
/
"V
.n
0..
40

30
-
"V • T=1000°C - no Zr02
20 y T=1000°C - 5% Zr(Q 20
"V T=1050°C - no Zr02
10 0 T=1050°C - 5% Zr(Q 10

a
2 4 5 6 7 8 9 700 800 900 1000 1100 1200
Time (hrs) Temperature (OC)
Fig. 17. The effect of zirconium oxide additions on the percentage zinc Fig. 19. The effect of temperature on the percentage lead removal from
removal from EAF dust at various reaction temperatures. EAF dust.
 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST 265

(a) l-ZnO
2-ZnOFe203
3-FeO
4-Fe
5-(CaO)zFez03
6-Halides
-NaCl
-KCl

(b) l-ZnO
2-ZnOFe203
Downloaded by [Monash University Library] at 11:59 02 July 2016

3-FeO
4-(CaO)ZFeZ03
5-CaOFez03

(c) l-ZnO
2-ZnOFe203
3-FeO
4-CaOFe04
5-(CaO )ZFeZ03
3

3
3 5

70 60 50 40 30 20 10
Z8

Fig. 20. X-ray diffraction (XRD) patterns of the EAF dust and iron briquettes after reaction times of (a) 1, (b) 3
and (c) 6 h. The briquettes were reacted at 950°C.

and 6 h, is shown in Fig. 20. The reaction temperature was
950°C. The ZnO and ZnO· Fe203 peaks on the patterns
decrease with time. Also, the calcium ferrite peaks, and the FeO
peaks increase with time. The halides in the samples, present in
the unreacted dust and in the sample reacted for 1h, were not
present in the samples reacted for 3 and 6 h. An unidentified
peak at a d-spacing of 2.18 A appeared in the pattern of the
sample that was reacted for 1 h. In previous research it has been
proposed that this is a non-stoichiometric iron-rich-oxide phase
containing calcium [33]. This was not observed in the patterns
of the samples reacted for longer periods. The solid solution
may have oxidized to form an identifiable calcium ferrite spinel.
 266 J. R. DONALD and C. A. PICKLES: ELECTRIC ARC FURNACE DUST

REACTION MECHANISM 100 r--,----.---,----,.------,------,.----,

T T=B50°C
v T=900°C
From the discussion of the results of the reaction of the EAF 80 • T=940°C
dust with iron, the following comments with regards to the
reaction mechanism can be made. • •
g •
1. The rate of removal of zinc vapour from the surface of the s::
60 •
briquettes was rapid, and thus, this did not limit the initial :3 •
o
::l
reaction at the briquette surface. -g 40
0::
2. The initial reaction rate was found to be strongly dependent
on the temperature with a relatively high activation energy
of 159.1 kJ/moi. 20

3. The initial reaction rate was not dependent on the length

of the briquette, but after the initial linear portion, the re- Oe---L--~--.L.----L_----l __ 1-----l

action rate increased as the aspect ratio (lId) decreased, for o 2 3 4 5 6 7

briquettes with aspect ratios (lId) less than one.
4. The initial reaction rate increased as the mass percentage
iron in the briquette increased; however, after the initial
period, the reaction rate was not dependent on the amount
Downloaded by [Monash University Library] at 11:59 02 July 2016
Time (hrs)
Fig. 21. Plot of the parabolic rate law (lines) and the experimental
points (symbols) for the reduction of the zinc oxide in the EAF dust
with iron.

of iron added over the stoichiometric amount.

5. The reaction rate increased with decreasing iron particle size,
and thus, increasing reactant surface area.
6. Lime additions promoted the reactions.
7. Zirconium. oxide additions promoted the reaction by
decreasing the amount of sintering.
The above Inentioned factors and physical evidence can be
employed to postulate a reaction mechanism. Initially, the reac-
tion rate is linear and the activation energy is high at 159 kJ Imol.
This indicates that initially the reaction is chemically controlled.
However, once a product layer has formed at the briquette
surface, the zinc pressure at the reaction interface increases and
the diffusion of zinc vapour out of the briquette becomes rate
limiting. The: reduction data have been tested for the degree of
fit to kinetic expressions, which were derived for diffusion-
controlled reactions. The parabolic rate law was used to model
the experimental results over the entire temperature range as
follows:
(12)
where C( is the percentage reduction, t is time and kp is a constant
that is a function of temperature. The parabolic rate law is
obeyed when the surface area is constant and the reaction rate
decreases because of the increasing thickness of the product
layer [34]. Plots of the model and the experimental points are
presented in Fig. 21. The model fit the intermediate temperature
runs very well; however the runs at lower and higher tem-
peratures are not as well represented by the model. This vari-
ation in behaviour may be due to incomplete formation of the
product layer at the lower temperatures and due to inhomo-
geneous diffusion through the product layer, caused by cracks
or sintering at the higher temperatures.
CONCLUSIONS
1. It was found that the reaction of the EAF dust was promoted
by increasing temperature, increasing iron additions,
decreasing iron particle size, and below an aspect ratio (lId)
of one. The initial activation energy for the process under
the standard experimental conditions was found to be
159 kJ Imol for the reduction of the zinc oxide in the EAF
dust with iron.
2. The EAF dust briquettes containing small amounts of iron
were significantly sintered at temperatures above I0008C.
Lime and zirconium oxide additions inhibited the sintering
by increasing the liquidus temperature of the EAF dust.
Thus, all three of these additives decreased the amount of
sintering, which promoted the reaction by reducing the par-
tial pressure of zinc \vithin the briquette.
3. A reaction mechanism is proposed that involves an initial
stage in which the reaction was chemically controlled. Once
a product layer has formed around the outer surface of the
briquette then the reaction is controlled by the diffusion of
zinc gas away from the reaction interface. The experimental
data were fitted to a parabolic rate law for diffusion-
controlled reactions.
Acknowledgemellls- The authors wish to thank the Ontario Centre for
Materials Research (OCMR) for financial support of this research. The
EAF dust was provided by CO-STEEL LASCO.
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(1990).
2. A. Little, Electric Arc Furnace Dust-1993 Orerl'ieu', prepared for
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