Minerals Engineering, Vol. 4, Nos 7-11, pp. 1003-1025, 1991 0892-6875/91 $3.

00 + 000
Printed in Great Britain © 1991 Pergamon Press plc

THE PROCESSING OF STEELMAKING FLUE-DUST: A REVIEW

R.L. NYIRENDA

Delft University of Technology, Faculty of Mining and Petroleum Engineering,

Department of Mineral Resources Technology, Mijnbouwstraat 120,
2628 RX Delft, The Netherlands

ABSTRACT

This review paper surveys technologies that are in use for processing
steelmaking flue-dust. Four categories of dust have been identified and used
in the discussion, namely: carbon steelmaking dusts with a high, low, and
intermediate non-ferrous metal content, and dust obtained from stainless
steelmaking. Adequate technology is found to be lacking for carbon steelmaking
flue-dust with an intermediate non-ferrous metal content.

The paper also considers the better known ideas which have been proposed,
either as alternatives, or as complementary aspects to existing dust treatment
options. The advantages and disadvantages of all examined dust treatment
processes are highlighted. In addition, the paper contains sufficient information
for an appreciation of the steel industry's flue-dust problem.

Keywords
Steelmaking flue-dust, recycling, processing, technologies, disposal

INTRODUCTION

The production of steel is generally carried out in one of three furnace types, the basic
oxygen, the electric arc, or the open hearth furnace. Irrespective of the type of furnace used
or grade of product made, steelmaking is accompanied by the emission of a large quantity
of dust which is carried out of the furnace by exhaust gas. Dust formation during
steelmaking has been considered by a number of authors [1-5], with Harding et al. [5] giving
a more detailed account, together with some suggestions on how to somewhat reduce the
amount produced.

Turbulence during steelmaking causes the ejection into the gas phase of some liquid steel
droplets and portions of any fine grained additives, such as slag formers, charged to the
furnace. Accompanying these into the gas phase, are elements which are volatilized from
the steelmaking bath. The degree to which the various species volatilize from the bath is
dependent on their vapour pressures. As steelmaking is conducted at temperatures in excess
of 1600 °C, virtually all Zn, Pb, and Cd present in the charge enter the gas phase. Small
amounts of iron and alloying elements (Cr, Ni, Mn, etc) are also volatilized. When the
temperature of the gas phase drops in the roof or hood of the furnace and in the ducts
conveying it, the fumed material oxidizes and condenses, largely, on particles mechanically
carried out of the bath. Interaction of the particles leads to the formation of physically and
chemically complex, micro-fine agglomerates.

1003
1004 R . L . NYmENDA

In a measure to prevent pollution, de-dusting units such as scrubbers, bag houses, and
electrostatic precipitators are used to clean furnace off-gases before they are vented into the
atmosphere. The extent to which gas cleaning is practised by individual steel plants may
differ considerably, but it is worthwhile to note that this is no longer a matter for plant
owners and operators to decide by themselves alone. Governments, and society at large,
have come to have a strong say in the matter [6-8].

Various authors [9-12] have given estimates of the quantity of dust generated during
steelmaking. Quoting on a dry basis, the estimates indicate that 10-20 kg of dust is emitted
per tonne of steel produced. Based on these emission figures, a conservative estimate gives
for the period since 1984, an amount of not less than 7 million tonnes of flue-dust
generated and recovered each year. This follows from the fact that in this period, the world
steel production has been in excess of 700 million tonnes per annum [13].

This paper reviews technologies in use, and some of those that have been proposed for the
treatment of the recovered dust. In order to better illuminate the problems involved with
the handling, processing, or disposal of steelmaking dust and any material arising from it,
the paper begins by giving brief details of some chemical, mineralogical, and physical
characteristics of the dust.

A vast quantity of other waste materials such as slags, mill scale, and refractory waste are
also produced from steel plants, but these are considered to be outside the scope of this
review and their recycle or disposal is consequently not discussed.

Chemical Composition of Steelmaking Flue-dust

The composition of steelmaking flue-dust is extremely variable. It varies not only from day-
to-day and from heat-to-heat, but also during the progress of a particular steelmaking
cycle. Thus in view of such variation, even if other problems associated with processing it
were to be ignored, the flue-dust collected would pose problems in maintaining stable
operating conditions in plants utilizing it.

It can be said, however, that the composition of the dust produced is mainly dependent on
the type of steel being made, and the nature and quantity of scrap and alloy additions which
inevitably constitute part of the charge.

Table 1 with data extracted from Keyser et al. [14] serves to illustrate the possible range
for some elements present in electric arc furnace dust. The table also shows the well known
fact that dusts arising from carbon steelmaking tend to be richer in zinc and lead, while
flue-dusts from stainless steelmaking are relatively low in lead and zinc, but richer in the
alloying elements Cr, Ni, Mn, etc.

In contrast with the tabulated composition of electric arc furnace (EAF) flue-dusts, basic
oxygen furnace (BOF) dusts have much lower amounts of non-ferrous metal oxides, and
contain for instance, 2-8% Zn and 0.2-1% Pb while the iron content is in the range 50-
80%. The much lower non-ferrous metal content is because these furnaces do not generally
have an external source of heat and can, at most therefore, only use a 1:4 scrap to hot metal
ratio [15]. Since BOF and EAF steelmaking account for about 57% and 27% of the world's
annual steel production, respectively [13], more flue-dust is produced in the steel industry
which has a low proportion, than that which contains a high amount of non-ferrous metals.
The balance of the steel produced comes from open hearths, furnaces whose scrap
consumption and consequently flue-dust composition may vary between that of the other
two furnace types.

Problems of Direct Recycling of Dust Arising from its Composition

In spite of the wide variation in composition, it is still apparent that the logical use for this
material should be in iron or steelmaking, since it is iron-rich. Direct utilization of the dust
for either of these purposes is however not possible for a number of reasons.
 Processing steelmaking flue-dust 1005

TABLE 1 Content range of selected elements present in electric arc furnace

flue-dusts from some USA plants [14]
Carbon Steelmaking Dusts Stainless Steelmaking Dusts
Element Range (Weight %) Range (Weight %)

Fe (Total) 24.9-46.9 22.2-35.9

Zn 11.12-26.9 1.77-6.22
Pb 1.09-3.81 0.23-0.78
Cd 0.03-0.15 0.006-1.79
Cr 0.06-0.58 2.01-10.1
Ni 0.01-0.12 0.15-3.34
Mo < 0.02-0.08 0.37-1.46
Mn 2.46-4.60 2.36-4.59
Mg 0.77-2.93 1.70-4.74
Cu 0.06-2.32 0.09-1.26
Ca 1.85-10.0 1.76-6.93
Si 1.35-2.49 1.36-4.83
CI 0.51-2.36 0.47-1.17
F 0.01-0.88 1.36-4.83
K 0.06-1.12 0.80-5.07
Na 0.29-2.31 0.47-4.60

In ironmaking, the major problem is that the dust contains intolerable levels of zinc and
other tramp elements like Pb, Cu, S, Na, and K as well as significant quantities of halides.
Zinc has been found to be the cause of many troubles in blast furnace operation [16], such
as refractory failure, scaffold formation in the stack, and complete filling of the gas
off-take. Consequently, feed to an iron blast furnace must have a very low zinc content.
Most specifications of iron ore suitable for processing in a blast furnace require, for
instance, that the zinc content be less than 0.01% [17]. Other undesired tramp constituents
are similarly unwanted even at low concentration levels because they also reduce the furnace
life or its efficiency [18], or are difficult to remove from the steel bath and lead to the
production of poor quality steels [9].

Recycling of the dust to steelmaking, causes the volatile components to recirculate. This not
only increases operating costs, but also gives rise to the build-up of impurities in the melt.
In addition, the dust requires a suitable agglomeration step prior to its recycle. Nevertheless,
recycling is a technique which finds some application as a means of increasing the
concentration of non-ferrous metals in the dust, prior to its withdrawal and treatment by
some of the technologies to be discussed.

Use of the Dust in the Zinc Industry

From the composition given in Table 1, it may be presumed that some dusts could be
processed by technology available in the primary zinc industry. This however has only been
possible in exceptional circumstances. The zinc content of steelmaking flue-dust is much
lower, and the iron content far much higher than that of calcines and sinters, leached and
smelted in the zinc industry, respectively.

High concentrations of iron are unwanted, whether in zinc hydrometallurgy or

pyrometallurgy. If the dust had to be processed in an acid leaching circuit, the presence of
a high amount of zinc as zinc ferrite would require that the dust proceed to the hot acid
leaching stage where even with the lower iron content of normal primary feeds, the problem
of iron precipitation has not to-date been quite satisfactorily solved. In the leading smelting
technology, the Imperial Smelting Process (ISP), the requirements of expensive metallurgical
coke would be prohibitive for the reduction of high amounts of iron oxides to wustite.
Furthermore, the relatively mild conditions maintained in this process to prevent the
formation of metallic iron, would result in very low zinc recoveries.
1006 R . L . NYIRENDA

Thus unless concentrated by some method, such as one of the high temperature reduction
volatilization technologies to be discussed, the raw steelmaking flue dust cannot in most
cases be economically disposed of through the zinc industry.

Problems of Direct Disposal of the Dust Arising from its Composition

In addition to the dissolution of alkalies, leaching tests have shown that chlorides and
sulphates of heavy metals present in steelmaking flue-dust are in most cases partly soluble
in water. A possibility thus exists for these species to contaminate ground water if the dust
is dumped on unprotected ground. Furthermore, as surface and rain water may vary over
a pH range, various governments have laid down procedures under which toxicity leaching
tests have to be carried out [19]. In the USA, for example, this has led to the classification
of electric arc furnace flue-dust as a hazardous material [20,21]. This is because higher than
stipulated amounts of toxic elements are leached out under the laid down test conditions.
The leachable toxic elements are lead, cadmium, hexavalent chromium, and in some cases
selenium [22].

Out of a recognition of the dangers of pollution, governments of many industrialized

countries have either restricted or are expected to restrict the manner of steelmaking
flue-dust disposal. Dumping will only be possible on specially constructed sites, protected
from ground water seepage and periodically monitored. It is estimated that in the countries
where this measure has already been imposed, the cost of preparing the material for
dumping, transporting it, and using the dumping areas is about US $50 per tonne of dust
[19]. This cost is further said to be steadily increasing as readily available dumping sites get
depleted and has recently been quoted for some areas at US $250 per tonne [23].
Circumstances have therefore made it imperative for the steelmaking industry to find
outlets for the dust, to curb its disposal or stockpiling.

Mineralogical Phase Distribution of Elements Present in Flue-dusts

Table 2 gives brief remarks on the phases containing the major elements present in
steelmaking flue-dust. Consistent with its mode of formation in an oxidizing atmosphere,
over 90% of the dust comprises of oxidic species. Na, K, Ca and Mg chlorides and fluorides
may range up to 5% of the dust, while the remainder consists of complex silicates plus
minor amounts of carbides, sulphides, and sulphates. As with the chemical composition,
substantial differences are to be expected between dust from carbon steelmaking and that
from stainless steelmaking. Nevertheless, in spite of the complexity and diversity of the
dusts, characterization studies based on XRD [9], mOssbauer spectroscopy [24], and
quantitative phase analysis [9,22] have led to the overall observations presented in Table 2.

The advantages and disadvantages, from a processing view-point, arising from the way the
elements are distributed in the various phases will become apparent in the discussion on
specific processing technologies.

Some Physical Properties of Steelmaking Flue-dusts

Table 3 gives a summary of some selected physical properties of steelmaking flue-dusts

and brief comments on the more common disadvantages the properties have on the
handling, disposal, and processing of the dust.

Categorization of Steelmaking Flue-dusts

In view of the differences in dust composition, any processing or recycling strategy

distinguishes between stainless steelmaking (SS) flue-dusts and dusts arising from carbon
steelmaking (CS). For the latter category, a further classification is made, namely, a
distinction between dusts which are low and those which are high in non-ferrous metals
(mainly zinc).
 P r o c e s s i n g s t e e l m a k i n g flue-dust 1007

TABLE 2 Mineralogical phase distribution of major elements

present in steelmaking flue-dusts
Element Phases Cont~inlng Element

Fe Fe304 is most prevalent phase. In it, Fe cations are replaced to

various degrees by Zn, Mg, Ca, Cr, Mn, etc. Some Fe is as a
metal and as a I F % 0 3.

Zn 50-80% as ZnO. Balance mainly associated with Fe in a mixed

zinc-iron ferrite spinel. Very small amounts of zinc may be as a
sulphide, silicste or aluminare.

Cd Distribution not well established, but possibly as for Zn

considering the similarities in most properties of the two elements.

Pb Mostly as an oxide. PbSO4 and PbCI~ are also present.

Cr, Ni Replace Fe in Fe304 spinel phase. Some Cr could be as Cr20 s.

Ca As CaO and CaCO 3 mainly. The balance may occur as a fluoride,

ferrite, or sificate.

TABLE 3 Selected physical properties of steelmaking flue-dust

and emanating problems in its handling, processing, or disposal
Property Normal Range for the Dust Common Problems

Panicle size individual partides mostly Poor recoveries in physical

less than 1 micron though
agglomeration prevalent
t9,221.
separation methods. Dry
dusts get air-borne;
Pollution. Feeding problems
in recycling. Difficulty of
solid-liquid separation after
leaching.

Bulk Density 1.1-2.5 g/cm~. The high side Relatively voluminous for
of the range is for wet disposal and storage.
collected dusts [9]. Difficult to re-introduce into
steelmaking bath.

Specific Surface 2.5-4 m2/g as measured by High reagent requirements

Area the BET method [22]. for processes based on
0.7 m2/g using Blaine air surface adsorbing reagents.
permeability apparatus [25]

Moisture Wet collected dusts, up to Wet dusts cake-up, are

Content 50% [9, 19]. Dry collected difficult to de-water and
dusts and stored under cover, filter. Dry dusts hang-up
up to 5% depending on CaO and are difficult to withdraw
content [26]. from bins and chutes.

The above classification is related to the product of major value which is obtained after the
dust is processed. These products are:
a) Zn (mainly) and Pb, from CS dusts high in non-ferrous metals. Flue-dusts qualifying
for this category must have an overall zinc content of at least 15%. This essentially
means flue-dusts from EAF steelmaking.
b) An iron-rich product, from CS dusts with low non-ferrous metals. In general, the
overall zinc content of dusts in this class must be very low, preferably less than about
1%.
c) A metal rich in alloying elements, from SS dusts.

Intermediate in composition between dusts giving rise to categories (a) and (b), a fourth
category of steelmaking flue-dusts can be distinguished.
1008 R.L. NYIRENDA

The categories of flue-dusts as outlined above form the basis for the discussion which
follows.

C A R B O N S T E E L M A K I N G DUSTS R I C H IN N O N - F E R R O U S METALS

A. High Temperature Processing

Technologies which have been successful for this class of flue-dusts are based on high
temperature reduction volatilization. Temperatures used are in excess of l l00 *C. Solid
carbonaceous materials are the more usual reductants, but gaseous reductants are also used.

The technologies differ in three fundamental aspects, all of which are related to the furnace
type. The differences are:

i. The manner of heat generation.

ii. The form in which the feed is charged to the furnace.
iii. The way in which the volatilized non-ferrous metal species are recovered.

Reduction and Volatilization

In all the processes, reduction of the oxides in the feed is effected by C, CO, and/or H 2.
ZnO is reduced to gaseous zinc; ZnFe204 is reduced to gaseous Zn and Fe304; Fe304 goes
to FeO or Fe, while PbO is reduced to Pb.

PbO is very easily reduced to Pb, but the vapour pressure of lead is very low below 1300
°C. It is volatilized at lower temperatures chiefly as lead sulphide and lead oxide, and to a
certain extent as lead chloride [27,28]. At least 90% of the lead and zinc in the feed, and
virtually all the cadmium are volatilized. A high percentage of chlorides (70-100%) and
alkalies (50-70%) initially present in the feed are also volatilized. Depending on the extent
of feed preparation, there is also a percentage of mechanically carried over material. FeO
forms a slag together with initially present, or added CaO and SiO 2.

Recovery of Volatilized Metals

Of the two methods available, one is to re-oxidize the volatilized material after it escapes
the charge bed, transporting it under suction and collecting it as a mixed oxide product in
gas cleaning installations [27-32]. The other method is to prevent the volatilized material
from oxidizing by using an air tight unit, transporting the material under suction and then
recovering it as metal in an ISP type of condenser [26,33]. The hot volatilized material from
the furnace is liquified by shock cooling it in a shower of liquid zinc which is maintained
in the condenser. The liquified zinc and lead are subsequently separated by taking advantage
of their lower mutual solubilities at lower temperature. The zinc recovered has some lead,
but conforms to the Prime Western zinc (PW) grade with < 1.6% Pb. Similarly, Pb recovered
has about 2% Zn but is also a saleable product.

When a condenser is used, hydrogen, water vapour, and dust proceeding into the gas phase
must be negligible to minimize the extent of re-oxidation of volatilized zinc [26]. This
requires that the feed be thoroughly dried, preferably agglomerated and indurated at high
temperature, and that the reductant used be of the type with a low hydrocarbon content.
The volatilized chloride forms with part of the zinc an unwanted dross in the condenser.
R e - o x i d i z e d zinc will also report into the dross or escape the condenser and be recovered
in gas cleaning equipment. Recycling of dross and oxidized zinc is practised, but still this
has an overall effect of reducing plant capacity and fuel efficiency, and increasing
maintenance costs. Cadmium ends up together with the zinc cast from the condenser.

When the volatilized material is recovered as a mixed oxide, further processing is required
to obtain the separate zinc and lead metals. This is done by hot briquetting the oxide and
using it as a feed to an Imperial Smelting furnace [29]. As the ISP utilizes a condenser for
 Processing steelmaking flue-dust 1009

the recovery of zinc, re=oxidation and chloride problems are as discussed above. It is
possible to de-halogenize the mixed oxide by washing it with sodium carbonate solution
prior to hot briquetting [34,35]. Instead of hot briquetting the mixed oxide, alternative
practice is to de-lead it in a kiln operated without reductant [28]. The products of this
second fuming stage are a high zinc containing calcine (clinker) and a lead-cadmium rich
f u m e also enriched with halides. By hydrometallurgical steps, separate recovery of the lead
and c a d m i u m in the f u m e is accomplished and the halides disposed of via a sodium
carbonate washing step. The zinc rich calcine is processed further by normal pyro or
hydrometallurgical routes.

Advantages and Disadvantages Common to High Temperature Processes

All reduction volatilization technologies lead to the production of inert slags from which
any residual toxic elements are hardly leached. The slags can therefore be used as sub-
surface material in construction or be dumped as a non-hazardous waste. Another advantage
common to the processes, is the diversity of zinciferous materials which they can utilize as
feed. Slags and residues from non-ferrous metal processing can all, in principle, be treated
to recover the contained volatile metals. At the high temperatures in use, even zinc initially
present as a ferrite is recoverable. The high temperatures used also mean that the reactions
are fast. In one reactor, and without solid-liquid separation and material transfer problems,
both aims of de-toxifying steelmaking flue-dust and eliminating Zn from it for subsequent
recovery are rapidly accomplished.

A common disadvantage of reduction volatilization technologies is that the iron rich slag is
generally not suitable for iron or steelmaking. For instance in the case of waelz kiln slag,
even after grinding to -300 microns and utilizing magnetic concentration, impurity elements
like sulphur and copper are still at unacceptable levels [29]. Metallic iron produced in some
of the processes is similarly contaminated [26,36]. Therefore, in spite of consuming
reductant and energy to reduce ferric iron to ferrous or metallic iron, little or no credit is
obtained for these products. Processes forming metallic iron "waste" more of the reductant
and energy.

In view of the above, capital and operating costs for the processes can therefore only largely
be defrayed by revenue from recovered zinc in the mixed oxide or condenser product. To
obtain a readily marketable mixed oxide, the feed to the processes must be blended to
contain approximately 15-20% zinc at a minimum [30]. The zinc content of the mixed oxide
produced is dependent primarily on the zinc content of the feed. From lean feeds, very little
can be done in the way of adjusting processing conditions so that a zinc rich mixed oxide
is obtained. Similarly when metallic zinc is directly recovered in a condenser, optimum
condenser efficiency is only possible from low volume, zinc-rich, volatilized material as
obtainable from rich feeds. In short, cost and technical factors exclude the use of feeds with
less than about 15% Zn. More commonly, the dust processed contains around 20-25% Zn
[371.

Required Scale of Operations of High Temperature Technologies

Without giving specific cost data, as such data is dependent on the type of process and
where it is located, Figure I shows the reciprocal relationship that exists between the unit
capital cost of a plant and its capacity. The main influence to the relationship being the
fixed costs which remain invariant even when the plant capacity changes. Unit operating
costs and plant capacity are related in a similar manner [30]. For favourable performance,
high temperature reduction volatilization technologies take advantage of reduced unit costs
at high plant capacities. Thus, for instance, the waelz kiln has been said to be uneconomic
at plant capacities less than 50,000 tonnes of feed per year when processing steelmaking
flue-dust with about 15% Zn [19,20,29]. Since most steel plants produce less than 5,000
tonnes of flue=dust per year [7], this has led to the operation of regional processing plants
which cater for a n u m b e r of steelmakers. Most of such plants are being run by companies
that have come to specialize in processing of waste oxides. Steelmakers are charged a fee for
their flue=dusts to be processed in these plants; the fee being higher the lower the zinc
1010 R . L . NYIRENDA

content of the dust is. A treatment charge of US $30-50 per tonne of dust has been quoted
for Europe [38], presumably for dusts with a zinc content of 20-25%. For the steelmakers,
disposal of the dust in this way is favourable if the treatment charge is less than the cost of
dumping the material. For the owners of the waste processing plants, the revenue from the
saleable products must cover the operating costs and give a reasonable return on investment.

Capital cost/annual plant capacity

\ \
\

Annual plant capacity (units of weight)

Fig.l Trend in the relationship between the unit capital cost of a plant and its capacity

Specific High Temperature Technologies

The processes which have been developed or adapted for this category of dusts, on the basis
of the principles outlined above, are set out in Table 4. The table excludes the numerous
high temperature processes which were examined at the laboratory scale in the past, some
of which may have been technically sound but which economics did not permit further
progression. This includes such ideas as single and two step vacuum fuming [39], reduction
volatilization in a shaft furnace [40] or extended arc flash reactor [41], and fuming in the
presence of chlorine [42].

Concerning the processes listed in Table 4, the waelz kiln process which is conducted in
rotary kilns measuring more than 3m in diameter and 40m in length, is well established and
clearly leads in terms of the number of plants in existence and the tonnage of flue-dust
processed. However, the newer technologies listed which all have stationary, more compact
reactors measuring less than 2m in diameter and 5m in height, and high smelting rates may
in time have a more dominant role to play. The electrothermic and half-shaft furnace
processes are however unlikely to gain any prominence, since even in the application for
which they were invented, their share of zinc production has always remained low [53,54].
The Sirosmelt Process, though designed for another purpose, has been included in the list
of high temperature processes because it is likely that the process could be extended to the
treatment of steelmaking flue-dusts.

Various modifications have been proposed to the waelz kiln process in the manner of feed
preparation or kiln operation so as to reduce accretion formation or lower the reductant
consumption, but basically the process remains the same. A recently proposed modification,
the Inclined Rotary Reduction System (IRRS) [55] is however worth further mention. An
IRRS plant is said to be under construction in Caldwell (USA), after the successful
performance of a demonstration plant in Saltillo (Mexico) in 1987.

The essential difference with the waelz process is that the IRRS (Figure 3) has additional
facilities so that the mixed oxide recovered in bag filters is pelletized with quality coal
powder and binder, and fed to a retort heated externally by kiln off-gases. Zn, Pb, and Cd
fumed from the retort is recovered in an ISP made condenser. After heating=up the retort,
the cooled kiln off-gas then proceeds to the bag filters for recovery of the contained mixed
oxide. In order to use the kiln off-gas to heat-up the retort, its volume is kept low by using
an oxy-gas (CH4/O2) burner for maintaining the kiln temperature.

TABLE 4 High temperature technologies for processing carbon steelmaking
flue-dusts rich in non-ferrous metals
Process and Description
1. Waelz Kiln Pracess [28,29,34,35,38]
Feed (pelletized): Fine flue-dust +
coke/coal powder + silica/limestone
flux.
Heat generation: carbon in feed +
auxiliary gas/oil burner at discharge
end, Max. charge T, 1100-1250 *C.
Products: Mixed oxide and dry slag.
.7- Tetronic~ Plasma Proe~x~ [33,36,44]
Feed (blend of fine dry materials):
Dust + fluxes + coal/coke powder.
Heat generation: Electrical energy,
DC argon stabilized arc between
cathode above charge and anode in
furnace hearth. Furnace T about
1500 "C.
Products: PW zinc;, Pb with 2% Zn;
molten slag; molten Fe. If selective
reduction used, no Fe forms,
3. Flash Furnace Process [30-32]
(Flame Reactor Process)
Feed: Fine dry powder pneumatically
injected. For most dusts fluxing is
unnecessary.
Heat generation: Pulverized coal or
gas fired, with 0 z enrichment.
Furnace T above 1600 ~ .
products: Mixed oxide & liquid slag.
4. Electric Furnace Process [26,46]
(Elkem Multi-purpose Furnace)
Feed (briquettod with H~O-free
binder): Dust + fine coke + silica
flux. (All needed dry).
Heat generation: Slag resistance to
electrical flow. Slag at 1500 *C.
Products: Zinc metal (PW grade); Pb
bollion (with 2 ~ Zn); molten Fe
(<20% of Fe in feed). IAquid slag.
5. Electrothermic Process [47,48]
Feed: Sintered dust + pea coke.
Before sinteriag, dust de-leadod by
roasting (1300 "C) in presence of
CaC12.
Heat generation in furnace:
Electrical energy mainly. Coke, for
reduction and current flow. Reaction
zone, 1350 *C.
Products: Pb-rich dust, from roasting
& sintoring. ZnO, by oxidation of
Z n ~ from furnace. Dry slag.
6. Half-Shaft Furnace P r o s , [49,50]
Feed (Briqnett~): Dust + Zn/Pb
residues + fine coal + binder.
Heat generation: Coal combustion
with pre-heated air.
produ~: Matte, from sulphides
present. Liquid slag. Mixed oxide.
7. Sirosmelt Proces~s [51,52]
Feed: Slag (or other feed material)
+ coal. (Optional addition of Pb to
collect Cu, Ag, Au into bullion).
Heat generation: Fuel oil/coal
combustion. Submersed injection,
during reduction/fuming stage. Bath
temperature, 1350 "C.
Products: Mixed oxide; molten slag.
(+ bullion, if Pb added),
• tpy = tonnes per year; all tonnes refer to tonnes of steelmaking flue-dust.
"" S = US dollars, at the value of the indicated year,
Processing steelmaking flue-dust
State of Development
Most widely used process.
Adapted for this purpose
since mid '70s. Used in
Eurnpe/Ameriox/Japan in
at learnt 13 plants. Plant
calm¢ttiu are of the order
of 50,000 tW* and higher.
(Shown in Figure 2)
Two commercial plants in
U S A of capacities 7,200
and 11,000 tpy. Sited in
Jackson aad Blytbeville,
respectively. Both
commissioned 1989. Same
furnace type used for
stainless steel dusts,
Sheffield. UK [45].
Prototype unit has been
tested (Monaox, USA).
50'000 tpy gas fired plant
being engineered
(Banlesville, USA).
Furnace in commercial
operation for rock wool
production (Iceland),
Demonstration plant hat
been operated for dusts
(Norway). Uses Imperial
Smelting Process Zn
condenser.
Plants initially built for
primary Zn industry,
Japan (Ryoho) plant,
45,000 tpy (35,000 tpy dust
used since 1974. USA
plant (Monaca), 100'000
tpy total (since 1980 an
unspecified 9b of this has
been flue-doxt).
Part of old Zn processin S
plants where furnaces
were orisinelly constructed
for Retort process
residues,
Development and
marketing since 1 9 8 0 ,
Initially for treatment of
old proee~ slags, has been
extended to non-ferrous
smelting flue-dusts. Said to
be suitable also for
processing neutral leach
residues of zinc plants.
Economics
1987,capita] cost for a
60,000 tpy plant about
S20m*" [19]. Operating
costs estimated as $85/t
(1988) for a 50'000 tpy
phmt [43].
Cost data for CS dust
proceM unavailable. Total
investment for S,000 tpy
SS dust prnee~ estimated
at £2.2m in 1986. (SS dust
proce~ ham no condemer).
In 1977, similar concept
had estimated operating
costs of $88/t for a 30,000
tpy plant [41].
1989 estimates, $5.3m. for
a 40,000 tpy plant; SLTm
for a 5,000 tpy unit.
Operating cost, $109/t.
Cost data unavailable.
Economic data not
available, Old plants
whose feed hat now
changed to include
steelmaking flue-dust.
Cost data unavailable.
Plants are part of old
primm'7 zinc production
works whose feed hat now
changed to include
steelmaking flue-dust.
Cost data unavailable.
However, capital and
operating costs are said to
be low,
1011
Advantages & Dixedvantagus
Feed preparation relatively
simple. Problem of accretion
formation/refractory
maintenance. F.~ceat usage of
carbon, thongh pan is recycled.
Favoured by chnap co~ULMixed
oxide needs further processing.
Direct recovery of metals.
Selective reduction mode, forms
corrosive FeO rich flngl; higher
refi~to~ costs. Aho CO2 hl~aar
in off-;at, lower Zn recovery.
Opereses between t o ~ and
selective reduodon~ Za recovery
(70%) presently, lower than for
other prneessns. Favoured by
hydro*electrlc power (HEP) use.
Stated as idea] for small scale
prooxssmg. Low cost carbon or
gus as fual. Mhed oxide nneds
furtherproox.i~ acquire o~.
but cost estimates include
Direct metal re.cowry. Fe metal
formntion, energy & reductant
waste. Elaborate feed
preparation. Favoured by HEP
availability, Furnace said to need
lower refractory maintenance,
frozen slag part of lining.
High purity ZnO product (98%).
High energy requirements for
matting, sintering, reduction
furnace. Expensive quality coke,
42% slntar weight used. Some
unused coke & uoxmaltod sinter
recycled, obtained as magnetic
separation taillngs.
Mired oxide produced. Lower
Zn recoveries. Productivity low
for single unit. Matte enables Cu
and All recovery, though matte
and slag not easily separated.
Transportable unit. Ideal for
small scale processing. Relatively
simple process. Submerged
injection, high smelting &
reduction rates but at cost of
lance wear. Mhed oxide requites
funber prneessin S.
1012 R.L. NYIRENOA

FURNACEOUST
r-- IHPELLER I I C°AL
' "L FLUX
, /
AIR /

FXHAUST -
...... .

ZINC
8A6HOUSE OXIDE ZINC PLASHA
FILTER CONDENSER FURNACE
Fig.2 Schematic diagram of the Tetronics Plasma dust treatment plant [33,36]

~ _~FILTEI!

IPbO,
I ZnO,
CdO, CO 2

~PELLETS
1
v~oua* ~ ~ t
I ,PLA,. !
FURNACE } I °°N°ENsEn ~
DRI |FLUXED| RESIDUE Zn, Pb, Cd
j METAL w
Fig.3 Flow diagram of the Inclined Rotary Reduction System [55]

A modification of the plasma process, the Sustained Shock-wave Plasma [23], has also been
proposed and is being investigated at the laboratory scale with the potential advantages of
offering a lower cost, mobile unit which would avert the need for dust transportation.

These modified processes are not substantially different from the original processes and
would therefore not be expected to be economic for dusts failing to qualify as feed to the
latter.

B. Hydrometallurgical Based Treatment Routes

A vast amount of research work has been done on the possibility of processing steelmaking
flue-dust by methods based on leaching. The impetus for such work has been the need to
develop a process that could be economic at lower throughput by averting the large energy
consumption of reduction volatilization technologies. As in pyrometallurgical processing, the
idea of developing an ideal process with residues recyclable to iron or steelmaking has
ebbed for this category of dusts which has a high non-ferrous metal content. The primary
aim is to de-toxify the dust so that the residue can be disposed of as ordinary waste material
 Processing steelmaking flue-dust 1013

without payment of high charges, and to defray costs for such processing by maximizing
credit from the sale of other process products.

Available information indicates, however, that up to now none of the proposed

hydrometallurgical based processes has resulted in a successful commercial operation. Of the
numerous conceptualized processes, three are examined in some detail below, chosen
because they have been well investigated and illustrate the problems generally faced by
hydrometallurgical processes.

1. The Caustic Leach Process I39,56-611

The Caustic Leach Process is based on the dissolution of zinc and lead oxides contained in
flue-dust, in hot (95 *C) concentrated NaOH (6-12 M) solution. The leaching step takes 1-
2 hours, with the dissolution of oxides proceeding according to Eqns. 1 and 2:

ZnO + 2NaOH = Na2ZnO 2 + H20 (i)

PbO + 2NaOH = Na2PbO 2 + H20 (2)

A distinct advantage of this leaching process is that hardly any iron goes into solution. The
major problem, however, is that of solid-liquid separation to remove the ultra-fine solid
particles from the relatively viscous solution. Lead is cemented out of the filtrate with zinc
dust, prior to zinc electrowinning. During electrowinning, zinc is deposited as a high purity
dendritic powder and NaOH is regenerated. Both metal products are in a readily marketable
form. Equation 3 describes the electrowinning step.

2Na2ZnO 2 + 2H20 = 2Zn + 4NaOH + 02 (3)

Of the investigations carried out into a Caustic Leach Process, one called the Cebedeau
Process resulted in a commercial facility in France in 1986 [58]. The plant however was
reportedly inefficient in some unspecified manner and discontinued processing of
steelmaking dusts within a short time [62]. The other major effort with a Caustic Leach
Process has been at Cardiff, UK, where a pilot scale plant has been run for a number of
years [57,61].

The Cebedeau Process utilized centrifugal filtration to achieve solid-liquid separation but
in the work on the Cardiff Process, researchers found that settling of solids after the
leaching step took days to start; centrifugal separation of solids was disappointing, while
chemical flocculants and conventional filters were unsuccessful. Their work has led to the
development of a solid-liquid separation technique which is based on settling of solids in
a high intensity magnetic field. Final solid-liquid separation is conducted by means of a
filter press. Zinc and lead recoveries by the Cardiff Process are said to be over 80 and 90%,
respectively. Unrecovered zinc is largely tied up as a ferrite. This zinc can be recovered by
the application of a reduction roasting step before leaching, but in this case the lead
recovery is low, as lead oxide is reduced to metallic lead. Therefore, in what is known as
the full Cardiff process, two-stage leaching has been proposed with an intermediate
reduction roast.

The behaviour of trace elements, including cadmium, during caustic leaching has not been
reported. The iron-rich residue is however said to be suitable for disposal, though
Dreisinger et al. [63] remark that for steelmaking flue-dusts with a high CaCO 3 and CaO
content, a toxicity test on the residue would give an excessively alkaline leachate.

The capital and operating costs for the caustic leach process have been stated to be as
follows:

i. $3.5m for a plant processing 12,000 tpy of electric arc furnace dust, with direct
operating costs of $170/t for the Cebedeau Process. (1986 US $). (As reported in
reference [63])
1014 R.L.NYIRENDA
ii. Capital costs of £3.4m for an 8,000 tpy facility, with direct operating costs of £ 184/t
of electric furnace dust for the Cardiff Process [61]. (1989 U K £).
111.
o o .

$14.4m for a plant processing 15,000 tpy of electric arc furnace dust, with direct
operating costs of $180/t for the process as proposed by Eacott et al. [59] (1984
Canadian $).

2. The UBC-Chaparral Process 163,641

This is a process proposed fairly recently in which meticulous care has been taken to ensure
that process residues fulfil even more stringent toxicity standards for residue disposal than
those currently in force. The process does not however aim to recover zinc that is present
in steelmaking flue-dust in the form of zinc ferrite.

The process makes use of an el~/borate flowsheet (Figure 4) with the following main steps:

i) Chloride removal by cold or hot water washing. Zinc, lead and calcium that happen
to go into solution are precipitated as carbonates by addition of carbonic acid or
sodium hydrogen carbonate.
ii) Leaching of free lime from the dust with acetic acid, to forestall high CO z
consumption during the zinc leaching step with ammoniacal-ammonium carbonate
solution. Calcium acetate is preferentially formed. Any Cd and Pb that may also be
present in solution are cemented out with zinc dust and filtered out.

2HAc + CaO = CaAc z + HzO, where Ac = CH3COO radical. (4)

Resin Water

• ~ WashWater Dust Water

WashWater

ZincContaining
Residue
C~a~iurnZil'~ ~ [ ~L] ,
Cementation
Sulphuri¢AciO

Procmttation

Arnmoma Zinc L ~ ' h

Dioxide~
Carbon ~

Zinc ~ Cementation ,]
Cadmium
Stem I--lira./'mm°"ia
Pttgioitation CarbonDioxide
Recycle ... L ~ ZincCarbonate
Fig.4 Flowsheet of the UBC-Chaparral process [63,64]
 Processing steelmaking flue-dust 1015

iii) Gypsum precipitation from the calcium acetate solution by the addition of sulphuric
acid.

CaAc 2 + HzSO 4 + 2H20 = CaSO4.2H20 + 2HAc (5)

Acetic acid is regenerated during the process. If no market is available for the
gypsum produced, it is said that the material could be disposed of directly.
iv) Ammoniacal-ammonium carbonate leaching of lime leach residues to solubilize zinc
oxide. A small amount of cadmium and lead are also dissolved, which are again
removed by cementation with zinc dust. Zinc is recovered from solution as a
hydroxide-carbonate mixture by steam stripping. This zinc product could be sold as
such, or leached in sulphuric acid and electrowon.
v) A clean-up leaching step conducted at the boiling point, during which most of the
lead and cadmium are removed from the residue with acetic acid and subsequently
cemented out with zinc dust. The Pb and Cd cement could be shipped to a lead
producer.
vi) A final clean-up step for the residue prior to its disposal. A strong acid resin is used
to remove any solution with metallic cations entrained in the residue.

Recoveries of the order of 60% Zn, 60% Pb, 85% Cd, and 100% Ca into the intended
products were achieved from carbon steel electric arc furnace dusts containing 20.5% Zn,
4.0% Pb, 0.18% Cd, and 12.5% Ca.

The inventors of the process give a preliminary cost estimate of $4.5-5.5 million for a
24,000 tpy plant and direct operating costs of $102-122 per tonne of flue-dust. (1988 US
$).
3. The Versatic Acid Process 1651

The process was initially proposed for recovering zinc from chloride-containing waste
solids, such as waelz kiln oxide, ash from galvanizing baths and flue-dusts from zinc
smelting. The concept is here examined from the point of view of processing steelmaking
flue-dust.

Versatic acid is a mixture of tertially monocarboxylic acids with the simplified formula
R1R2C2H3COOH , where R 1 and R 2 are alkyls with 3 or 4 carbon atoms. The formula may
be further simplified to VH where V is the versatic radical, R1R2C2H3COO. In leaching
applications, versatic acid is dissolved to 30 vol % in a paraffinic fraction, such as kerosine.

For the materials for which the process was developed (all low in iron and high in ZnO
content), zinc is leached into the organic phase in the extraction stage according to Eqns.
6 and 7. Halogens entering the organic phase are removed by water washing. During the
next process step, stripping, the zinc-loaded organic phase is contacted with a mineral acid
to transfer zinc to an aqueous solution and to regenerate the organic phase for recirculation
to the leaching stage. If sulphuric acid is used for stripping, then an aqueous solution of
zinc sulphate results [Eqns. 8 and 9] which proceeds for zinc recovery by electrowinning.

Extraction: 2VH(o r g ) + ZnO(sotid ) = [ZnV 2 + H20 ] (or

g) (6)
Extraction: VH(org ) + ZnO(sotid ) -- [ZnOHV](org ) (7)
Stripping: [ZnV2] (org ) + H2SO4 = ZnSO4 + 2VH (or g) (8)
Stripping: [ZnOHV](org ) + H 2 S O 4 = Z n S O 4 + VH(org ) + H 2 0 (9)
To be applicable to the treatment of steelmaking flue=dust, the process would presumably
need a second leaching stage in which the residues of the organic leach would be digested
in hot concentrated acid. The technical and economic feasibility of such a modified process
has been examined from the stand-point of zinc recovery from the roasted calcine of
primary zinc plants [66]. The purpose of the second leaching stage would be to dissolve zinc
present as the ferrite, according to Eqn. 10.
1016 R . L . NY1RENDA

ZnFe204 + 4H2SO 4 = ZnSO 4 + Fe2(SO4)3 + 4H20 (1o)

The aqueous phase with zinc and iron sulphate would be contacted with the organic phase
in a second extraction stage. Iron would preferentially accumulate in the organic phase
while zinc would be in the aqueous phase:

6VH(or9 ) + Fee(SO4) 3 = 2V3Fe(org ) + 3H2SO4 (ll)

Zinc present in the aqueous phase would be amenable for recovery by electrowinning. The
iron in the organic phase could be removed and the organic phase recycled by one of several
methods as examined by Collier et al. [66]. For example by HC1, H2SO 4, or hydrolytic
stripping.

When compared with other methods for zinc recovery from roasted calcines, the Versatic
Acid Process was found to be more expensive; for example nearly twice as expensive as the
Jarosite process. The high production cost of the process was related to the high energy
consumption for iron removal from the system (approximately 40% of the total production
cost).

Another draw-back of the Versatic Acid Process if applied to steelmaking flue-dust would
be the difficulty of solid-liquid separation after the hot acid leaching stage. Furthermore,
the residue of this step which would have to go out of the process circuit would contain Pb.
This would have to be recovered by additional steps before residue disposal.

Other Proposed Hydrometallurgical Processes

Table 5 lists other leach liquors which have been investigated for the purpose of processing
steelmaking flue-dust. Detailed descriptions of proposed processes based on these leachants
can be found in the original references or in a publication which recently reviewed most of
them [63]. Miscellaneous other methods based on leaching have been investigated, such as
leaching with CI 2 saturated water [67]; wetting with ferrous sulphate, followed by baking
at 600-650 *C and then water leaching [10]; mixing with sulphuric acid, and then roasting
prior to a water leaching step [68]. All these processes either leach a low amount of zinc,
contain lead in the residue, or lack selectivity and dissolve large fractions of the sample.

Not surprisingly therefore, most of the conceptualized hydrometallurgical based processes

are not in a position to attract investment that could lead to the setting up of commercial
units.

CARBON STEELMAKING DUSTS LOW IN NON-FERROUS METALS

Flue-dust belonging to this category is utilized in recycling schemes. Consequently the less
its zinc content, the more suitable the dust is for treatment. The maximum zinc content
required in the dust has been variously stated as 1% [70, 80], 2.5% in exceptional
circumstances [11], and 2% (total of Zn & Pb) [40]. Technologies used for processing it,
essentially agglomerate the dust into a form suitable for handling, transportation and
eventual feeding to the blast furnace. Agglomerates produced must therefore have a high
mechanical strength. Their production involves either high temperature induration or
hardening procedures based on the use of binders.

By far the most important agglomeration processes in use are sintering, pelletization, and
briquetting. Cold bonding processes with binders such as portland cement, lime and silica
have however also attained positions of local importance [81,82].

Even in the case of sintering, in which coke breeze is added to the dust and a high
temperature is used for the agglomeration process, insignificant impurity removal is
accomplished [18]. This fact more than anything else, restricts how much steelmaking flue-
dust can be incorporated into agglomerates for use in ironmaking. Other problems inhibiting
 Processing steelmaking flue-dust 1017

the extent of dust utilization at the agglomeration stage of the iron blast furnace feed, are
related to the difficulty of handling and adding the dust without spillage, plugging of bins,
choking of chutes, or mechanical problems with plant equipment conveying it. A number
of techniques have however been reported in the literature for minimizing the handling
problems [80,83].

TABLE 5 Leachants for other conceptualized hydrometallurgicai processes

Leachant/Leaching Conditions Disadvantages

1. Sulohuric Acid [69-71]

Final pH = 2-3; T < Boiling point; Lead in residue as PbSO 4. Only Zn

t < 4 hrs; Pressure, atmospheric. initially as Z n O leached.

Final pH = 1-1.5; T = 225-300 °C; Lead as PbSO4 in residue. Despite

t = 1 hr; 02 Pressure = 1.7-17 atm. high process cost, residue not
recyclable - hematite contaminated.

2. Hydrochloric Acid [72]

Final pH < 1; T < Boiling point; Nearly all dust dissolves [73]. Fe
Pressure, atmospheric. precipitation & impurity removal
from filtrate costly. Ferrous residue
with some co-precipitated PbC12.

3. Mixture of HCI & H2_~Q4_ [74-76]

H2SO 4 sufficient for all Ca & Pb Zinc ferrite not leached. Additional
sulphation. Final pH = 1-4; steps for PbSO 4 removal from
T < Boiling point; Pressure, residue needed.
atmospheric, t = 4 hrs.

4. CO. Saturated Water [77]

Leachant further acidified with SO z Low % Z n leached. Zinc in ferrite

or small amount of mineral acid. not recovered. Requires autoclave.
Low temp; Pressure = 15-40 atm. Pb remains in residue.

5. Ammonia-Ammonium Carbonate [78]

High concentration CO 2 & NH a. Zinc present as ferrite not leached.

Pressure, atmospheric. Low temp. Most Pb remains in residue.

6. Ammonium Chloride [79]

Cone. = 25-30 wt % NH4CI. Zinc present as ferrite not leached.

Temp = 90-100 *C. Some Pb (of unknown leachability)
remains in residue.

Dusts produced in BOF converters when only in=house scrap or selected low zinc scrap is
used are particularly suitable as they generally contain less than 0,1% Zn [84].

Feeding of agglomerates to steelmaking is also practised. In this case agglomerates need not
be of a very high mechanical strength and green balling with water as a binder may be
sufficient. Up to about 15% carbon is added to the dust before agglomeration to serve as a
reductant for oxides when the agglomerates are introduced into the steel bath. For high lime
containing dusts, special green bailing techniques have also been developed to counter the
problem of pellet disintegration due to hydration [85].

ME 4:7111=Y
1018 R.L. NYIRENDA

The effect of feeding agglomerated dust to steelmaking is the same as discussed in the next
section.

CARBON STEELMAKING FLUE-DUSTS WITH AN

INTERMEDIATE NON-FERROUS METAL CONTENT

The greatest problem to the steel industry is posed by dust falling in this category. The
options currently available for processing it can only absorb a small fraction of the dust,
thus leaving copious amounts to be dumped. The state-of-the-art for this category of dusts
is considered in the next paragraphs, together with an assessment of the potential other
treatment options hold.

Recycling to Iron and Steelmaking Units

A very limited amount of the dust can be used in the iron blast furnace by incorporating
it at the agglomeration stage. An equally low amount can be blended with dust of a much
higher zinc content, and the resulting mixture, used as feed to one of the reduction
volatilization processes. A somewhat higher fraction is recycled to steelmaking units. By
repeated recycling of collected dust, back into steelmaking units, it is possible for the zinc
content of the dust to be upgraded to a level where the dust can be withdrawn and
processed by high temperature processes. The following limitations, however, hamper this
approach:

i. Build-up of impurities. With each recycle, the amount of sulphur and non-ferrous metals
in the collected dust increases. The recycle of dust with high impurity contents would affect
the quality of steel produced [9].
ii. Available dust collection facilities. The amount of dust to be collected increases with
every additional recycling step. At high dust-loadings the efficiency of dust collection
systems is impaired [19].
iii. Reductant and energy requirements. Besides energy for melting, the dust requires
reductant. This is not only for the contained iron oxides, but also for non-ferrous metals
which require reduction prior to volatilization. Repeated recycling of collected dust is thus
costly [20].
iv. The method of charging recycled dust to the furnace. With its fine particle size and low
bulk density, feeding of as-collected dust back to the furnace has only been possible by
bottom injection into a converter. The more usual practice requires agglomeration of the
dust prior to recycle. Even then, special charging techniques are required to prevent the
agglomerates from disintegrating and getting ejected violently upon addition to the molten
bath [85].

Direct Reduction Processes.

High temperature reduction of dust agglomerated together with solid carbonaceous material
was the general approach considered some years ago. Pilot scale plants, mainly rotary kilns
were set up [86-91]. It is reported that many iron and steel plants in Japan did even get to
utilize these processes on a commercial scale for some years [19]. The objective of direct
reduction processes was to volatilize zinc, lead, chlorides, and sulphur present in the feed
so as to obtain a product with a high percentage of metallized iron. After cooling it in an
inert atmosphere, this material was intended for use in iron or steelmaking while the small
amount of recovered zinc-lead mixed oxide was to be processed or sold as a by-product.

These processes were however aimed at dust mixtures with very low zinc contents of less
than 3%. For this application the processes were successful, but even then, at a cost of
maintaining the feed at a temperature in excess of 1150 *C for a few hours. Due to the
low value of the products and extremely high energy costs, this processing concept did not
progress further.
 Processing steelmaking flue-dust 1019

Physical Separation.
The role of physical separation methods in the processing of flue-dusts would be to provide
a relatively inexpensive method of separating the ferrous and non-ferrous components for
subsequent treatment by other technologies.

It is well known that zinc and lead tend to concentrate more in the finer size fraction than
in the coarse range [21,25,92,93]. This has given rise to the installation of collection systems
or hydrocyclones in most BOF plants which permit the separate recovery of coarse dust and
sludge from fines. Typically, the coarse dust and sludge amount to less than 40% of the total
dust and contain agglomerates coarser than 60-100 microns [19,84]. The zinc content of this
material is less than 1% which makes it recyclable, but most of the remaining dust is
transported to dumps or placed in stockpiles. The magnitude of the dust impounded in this
way can be gauged by considering that the total amount of flue-dust arising from BOF
steelmaking was estimated at 4.6 million tonnes for the year 1985 [19]. A similar physical
separation method for EAF dusts has not been possible as even a size separation at 8
microns does not achieve any concentration of zinc in the fine fraction [25].

Up to the present time, other physical beneficiation methods have also not been of much
practical value in achieving significant separation of zinc and lead from the ferrous
components. Due to the fine particle size, gravity methods have been found unsuitable
[25,93]. The potential floatability of zinc oxide from iron oxides was indicated [9,92], but
a more detailed study found that dispersion which is a pre-requisite to successful flotation
needed impractically large amounts of dispersant (15 kg/tonne) due to the high surface area
of the dust [25]. Of the two dispersants tested, sodium silicate and sodium triphosphate, the
latter was found to perform better. The large amount of dispersant required was also taken
as an indication that flotation or selective flocculation would also have excessive reagent
consumptions. Flotation methods better suited for beneficiation of fines, such as oil and
flocculate flotation, have not been tried out but even these methods would require high
amounts of reagents. The increase in the quantity of conditioning reagents as the particle
size of the material to be floated decreases has been stated as a phenomena which may
possibly be never overcome [94].

Magnetic separation has also been considered [9,25,93]. At room temperature, magnetite is
ferromagnetic while zinc ferrite is paramagnetic and zincite diamagnetic. It is therefore
possible in theory to achieve useful separations on the basis of magnetic properties. The
problems encountered in practice include the following: i) Particles exhibit electrostatic
attraction, so that wet magnetic separation is necessary, ii) zincite has iron and manganese
in solid solution so that it is not possible to recover a non-magnetic zinc rich product, iii)
zinc substitutes for ferrous iron in magnetite and for a substitution of up to 50% of the
ferrous ions, the saturation magnetization of the product is comparable to that of magnetite.
Due to the last two factors, high intensity magnetic separation is out of the question while
the prospects for low intensity separation are quite limited.

Thus, in general, due to the fine particle size of the dust and the mode of occurrence of
zinc and iron, physical separation methods have to-date not played a major role in the
processing of steelmaking flue-dusts.

Chemical Stabilization

Various proprietary methods have been developed for chemically immobilizing heavy
elements in the dust, to yield material suitable for disposal as a non-hazardous waste [95].
Stabilization is based on the use of plastic resins, portland cement, water glass, or bitumen.

In general, these processes have relatively low investment and operating costs. For example
one stabilization option examined by Arkelow [7], comprising of pelletizing the dust with
portland cement and sodium silicate, drying, and disposal of the pellets, had an estimated
capital cost of US $400,000 for a 5,000 tpy plant while operating costs were put at US $35/t
1020 R.L.NYIRENDA
of dust. Therefore, when recycling of flue-dust or economic resource recovery from it is
not possible, chemical stabilization may at present appear attractive.

It is worthwhile to note however that when chemical stabilization is used, reagents are
consumed without yielding any valuable product and the long term stability of the resulting
product may be unknown. Furthermore, if an economic process does become available in
future, resource recovery from the stabilized material may be hindered by some of the
additives used.

Circulating Fluid-bed Process (Figure 5)

Cyclones

Dust~_ [[G÷clasecoo!i
anlnngg
Coal~
Air _ ~ r I
Ret
urn
Coke :n/Pb-Oxlde
CFB-Roactor
Recycling
gas

IC*''r I Excess gas

Fig.5 Flowsheet of the Circulating Fluid Bed process [38]

Development work is in progress to adapt to the processing of dusts with relatively low
amounts of zinc and other non-ferrous metals, the Circulating Fluid Bed-technology (CFB)
which is used in power stations [38]. The goal of the new process is similar to that of the
Direct Reduction Processes discussed above. Successful laboratory scale tests are said to have
been conducted, on the basis of which construction of a 20,000 tpy demonstration plant is
planned [37,38].

Estimates indicate that for a 200,000 tpy CFB plant, capital costs will be in the order of
$30-55m, with direct operating costs of about $80/t of dust. If this technology proves
successful, it will go a long way in averting environmental problems associated with
dumping and contribute to resource conservation. It is unclear, however, what the maximum
zinc content of the dust is which can be processed to enable the metallized iron product to
be recycled to iron or steelmaking units. Presumably this is about 3% which is cited by Kola
[38] in the projected mass balance for a 200,000 tpy plant. In which case, a lot will still need
to be done to evolve practice that will curb dumping of steelmaking flue-dusts with an
intermediate zinc content.

STAINLESS STEELMAKING FLUE-DUST

Recycling back to the furnace, of flue-dust from stainless and specialty steelmaking is more
readily accomplished [19,20]. Green pellets or briquettes are usually strong enough to be
 Processing steelmaking flue-dust 1021

charged. Alternatively, dust injection into the slag layer is utilized. Energy and reductant
costs arising from recycling are not as prohibitive as with carbon steelmaking dusts due to
the lower amount of non-ferrous metals in the dust and the higher value of alloy units
recovered [96]. Nevertheless, recycling is still subject to similar disadvantages as those listed
for carbon steelmaking dusts. This has given rise to new processes using separate furnaces
to achieve high temperature, carbothermic reduction of the dust.

Available processes are based on plasma technology or the use of submerged electrode
electric furnaces. All the processes use sufficient energy and a low sulphur source of
carbon, to completely reduce the dust. Molten metal, a liquid slag (facilitated by flux
additions), and a gaseous phase with zinc and other volatiles, are the products. The
volatilized species are collected as a mixed oxide in bag houses or similar devices and
supplied to zinc producers. The low amount of zinc in the off gas does not justify use of
a condenser for direct metal recovery. At least 85% of the Fe, Ni, Cr, and Mo in the feed
are recovered into the carbon saturated metal (ferro alloy) produced, which is cast and
recycled to steelmaking units while the slag produced is suitable for disposal.

The better known process utilizing submerged electrodes, is the Inmetco Process [97], which
has an associated rotary hearth furnace for partial reduction and strengthening of pellets
before they are introduced into the electric furnace. A 50,000 tpy facility has been in
operation since 1978 (Ellwood City, USA). In the more usual electric furnace practice, green
agglomerates are charged straight into the furnace [19].

Of the two types of commercial plasma units available, one is the Tetronics plasma furnace
which is similar to the furnace used for carbon steelmaking dusts. A plant capable of
processing 8,000 tonnes of flue-dust per year by this technique has been in operation since
mid-1989 in Sheffield, UK [45]. The other, is the ScanDust (Plasmadust) process [98,99]
which was commissioned in 1984, originally for high zinc dusts, but which has been adapted
to the treatment of stainless steelmaking dusts due to condenser problems with the earlier
application [38]. This plant, which is in Sweden, has a capacity of about 50,000 tpy and is
operated on a toll basis. Its capacity falls just under the total dust tonnage produced by
stainless steelmakers in Western Europe.

From the short assessment given above, it appears therefore, that adequate technology is
available which could be economically used to avert disposal of stainless steelmaking
flue-dusts.

CONCLUSIONS

Led by the waelz kiln, high temperature reduction volatilization technologies have clearly
established their capability of processing carbon steelmaking flue-dust, yielding slags which
are environmentally acceptable for disposal. The cost for such processing is off-set by the
value of the zinc in the recovered product, which necessitates that the feed contain at least
15-20% Zn. The present dominance of the waelz kiln will in time be challenged by some of
the newer processes which have higher smelting rates in compact reactors, and are
economical at lower throughput.

Carbon steelmaking dust containing less than about 1% zinc is more readily handled by
agglomeration and recycling to iron or steelmaking units.

Carbon steelmaking dust with an intermediate zinc content, which by far exceeds the other
categories of steelmaking dust produced, still finds its way into land-fills for want of an
economic technology. However, if the Circulating Fluid-bed Technology currently being
developed proves economic, it will go a long way in averting environmental problems
associated with dumping this material and contribute to resource conservation. Meanwhile,
flue-dust may be chemically stabilized prior to its disposal, in spite of the negative aspect
of this practice in not recovering any valuable product.
1022 R.L. NYIRENDA

Stainless steelmaking flue-dust has not been particularly difficult to recycle due to the high
value of contained alloying units. At the same time, processes utilizing high temperature
carbothermic reduction in separate furnaces are available.

In all the strategies for processing steelmaking flue-dust, physical separation methods have
to-date played little or no role, due to the fine particle size of the dust and the intimate
association of the contained ferrous and non-ferrous components. Similarly, in spite of the
vast research that has been done into hydrometallurgical based processes, it is yet to be seen
whether leaching concepts will lead to successful commercial dust treatment facilities or
make a contribution to the processing of steelmaking flue-dusts.

Finally, the newer approach of scrap pretreatment which seeks to recover non-ferrous
metals from scrap before its use in steelmaking deserves mention as a potential solution to
the flue-dust problem [100,101].

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