GENERAL OVERVIEW

OF
METALLURGICAL
SLAGS AND DUST

For academic purpose only

OUTLINE
01 Slag

02 Slag Type

03 Ferrous and Non Ferrous Slag

04 Incineration Slag

05 Slag Processing

06 Flue dust and Processing

SLAG
SLAG
Slag phase is generated, mainly from the addition of
mixtures of oxides and fluxes and is also composed of
reaction products like those resulting from the
oxidation of charge materials and the dissolution of
refractories.

The main slags are classified in three types:

Ferrous slag Non-ferrous Incineration

slag slags

Example: Blast
Example: Copper Example: Fly ash,
Furnace slag, Steel
making slag etc. slag, etc. Bottom ash, etc.
 Slag Type
According to the melted metal type According to the cooling method

Production process of blast furnace and steel slag Production process of copper, nickel, lead, lead-zinc, and zinc slag

Ivanka netinger et. al. Characteristic and uses of steel slag in building construction. WP. 2016
Ferrous Slag
BLAST FURNACE SLAG
• Blast furnace slag is a nonmetallic coproduct
produced in the process in the production of iron
from iron ore or iron scrap.

• It consists primarily of silicates, aluminosilicates, and

calcium-alumina-silicates

• These products include

1. Air-cooled blast furnace slag (ACBFS)
2. Expanded or foamed slag
3. Pelletized slag
4. Granulated blast furnace slag
General schematic of blast furnace operation and blast furnace slag production(courtesy,
Mr.M.P.Sudbury)
PRODUCT OF SLAG FROM BLAST FURNACE
AIR-COOLED
BLAST
FURNACE
SLAG (ACBFS)
Liquid slag slowly cooled
under ambient conditions
A crystalline structure is
formed, and a hard, lump
slag is produced, which can
subsequently be crushed
and screened
Crushed ACBFS is angular,
roughly cubical, and has
textures with conchoidal
fractures.
Expanded or
Foamed Blast
Furnace Slag
Liquid slag is cooled and
solidified by adding
controlled water, air, or
steam.
Crushed expanded slag is
angular, roughly cubical in
shape, and has a texture
that is rougher than that of
air-cooled slag
The porosity of expanded
blast furnace slag aggregates
is higher than ACBFS
aggregates
Granulated
Pelleted Blast
Blast Furnace
Furnace Slag
Slag
Liquid slag is cooled and Liquid slag is cooled and
solidified with water and air solidified by rapid water
quenched in a spinning quenching to a glassy state
drum
Pelletized blast furnace slag The physical structure of
has a smooth texture and granulated slag depend on
rounded shape. the chemical composition of
the slag
The porosity of expanded
blast furnace slag aggregates
is higher than ACBFS
aggregates
 BLAST FURNACE SLAG

Typical Chemical Composition of Blast Furnace Slag (Ontario Ministry of natural Resources,
Toronto, Canada, Mineral Aggregate Conservation, Re-use and Recycling.)

Typical Physical and Mechanical Properties of Blast Furnace Slag (From American Association
of State Highways and Transportation Officials, Standard Specifications for Materials "Blended
Hydraulic Cements" AASHTO M240-85, Part I, 1986)
Composition and Mineralogy of Steelmaking Slags
• Steel slag occurs in four classes: Typical compositions of such slags are shown in tables:

1. Basic converter slag : low phosphorus and high

phosphorus pig iron slags Chemical Composition of Calcium Silicate Slags (Akbari and Pickles, 1998)

2. Electric furnace slag

3. Pig iron desulfurization slag
4. In-ladle processed steel slag

Chemical Composition of Calcium Phosphate Slags from Various Converters (Akbari and
Pickles, 1998)

Minerological Phase Identified in Steelmaking Slags (Bjoerkman et al, 1996)

Non-Ferrous Slag
Composition and Metal Contents of Non-Ferrous Slags
The non-ferrous slags can be broadly divided into high Analyses of base metal content in non-ferrous slags vary
iron (copper and nickel sulfide smelters), high magnesia widely depending on the smelter feed characteristics and
(laterite, a complex nickel silicate ore), high lime (lead operating practices
smelters) and platinum group elements in an
Examples of Residual Base Metal Content of Non-ferroui Slags (Sudbury and Kemp, 2006)
intermediate position.

Variability of Non-ferrous Slag Composition (Sudbury and Kemp, 2006).

Physical properties of various nonferrous slag
Copper and Copper Slag production in pyrometallurgical process
Incineration Slag
PRODUCTION OF NON-METALLIFERROUS SLAG
A novel system called "Para-Eco Incinerator Ash Processing
System" has been developed by Takai and coworkers (2003) to
produce non-metalliferrous slag and to improve recycling of ash
produced from municipal solid waste

Summary of material flow in the para-Eco Incinerator Ash Processing System

(Takai et al, 2003)
 METAL
RECOVERY
FROM FLY
ASH
METAL RECOVERY FROM FLY ASH
Fly ash contains many heavy metals, especially zinc,
lead and copper. There is potential to recover them and
reuse as resource materials. Several techniques have
been investigated to achieve this goal.

1. Separation by Segregation Reaction 2. Metal Recoveries from Secondary Fly Ash

Stages: • Secondary fly ash is generated from the melting of

• Fly ash is directly heated in a controlled inert
atmosphere, using nitrogen gas and then chlorinated by
hydrogen chloride gas
• The metal chlorides formed are reduced by hydrogen,
which is produced by reacting carbon with water
• The metals deposit on the surface of carbon and are
recovered by separating carbon froth flotation
• The waste gas is quenched to suppress the generation
of dioxin
primary fly ash.
• Processing of secondary fly ash to recover zinc and
lead has been done by pyrometallurgical operation
using Mitsui furnace system
• Zinc present as fenite (ZnFe2O4) is reduced to zinc
vapor and then oxidized by excess oxygen to produce
zinc oxide. Lead is similarly recovered.
Slag Treatment
SLAG TREATMENT TECHNOLOGIES
Most steel mills process the slag as follows: The rate of generation and treatment practice associated with
various slags are summarized in Table bellow.
1. The slag is allowed to cool
2. Cranes with magnets sweep the slag to
recover the large pieces of steel which are Slag treatment

recycled back to the furnace

3. The remaining swept material is fed into
magnetic separator and screened to further
recover residual metallics for recycling
4. The remaining slag is sold as aggregate,
landfilled or stockpiled.
METALLURGICAL APPLICATIONS

01 02 03

Blast Furnace Sinter Production Slag Regeneration

Recycling
It is possible to use Use of steelmaking slag The possibility of recycling slags inside a steelmaking
such slag to recycle in sinter production plant is an attractive proposition as it would result in
back to the blast conserves charge a waste-free steelmaking process
furnace resulting in materials for pig-iron
savings in iron ore and smelting. However, it is limited by the high phosphorus
also flux materials like content in the steel making slags,
limestone or dolomite
 METAL
RECOVERY
FROM SLAG
RECOVERY OF METAL VALUES FROM SLAG
1. Recovery of Iron and Iron concentrate 2. Vanadium

Recovery of vanadium value from a ground slag (-100

mesh) has been described by Suri and coworkers (1992).
The process consists of thorough mixing with requisite
quantity of soda ash and roasting at suitable temperature
in the presence of small quantity of potassium chlorate
(KClO3) and air in a rotary furnace.

4 FeO.V2O3 + 4 Na2CO3 + 5 O2 ➔ 4 Na2O.V2Os + 2 Fe2O3 + 4 CO2

The optimum conditions for roasting to achieve

maximum leaching of 98 % of the vanadium value present
in the slag are, 20 % soda ash and 5 % potassium chlorate
Recovery of iron and iron minerals from steel slag (Shen and Forssberg, 2003)
by weight of the slag, 800 °C temperature and reaction
time of 2 hours.

Yu and coworkers (2004) have attempted to recover

vanadium from converter slag by slow cooling which
causes the vanadium compounds to concentrate in a
distinct phase, from which they are recovered.
 RECOVERY OF METAL VALUES FROM SLAG

3. Manganese, Niobium and Tantalum

A process to recover niobium, manganese and phosphorus from steel slag and convert them to make an alloy and
process the remaining slag for use as construction material has been described by Rong (1994). The slag is
reduced in a blast furnace, which produces liquid iron containing high grade niobium, manganese and phosphorus.
It is taken to a revolving furnace for smelting. The rich slag discharged from the revolving furnace is taken into an
electric furnace where it is s melted into alloy. The byproduct blast furnace slag is used as cement material and
firming agent. The electric furnace slag is used as raw material of refined manganese.

Recoveries of niobium and tantalum from tin slags by chlorination has been described (Gaballah et aL, 1997). Iron,
calcium, manganese and aluminum are first removed by leaching, (acid or successive acid and base). Then, the
niobium and tantalum concentrate is subjected to chlorination at 500-1000 °C for 24 h with (chlorine + nitrogen)
or (chlorine+ carbon monoxide + nitrogen). Niobium and tantalum oxides in the concentrate are converted into
respective chlorides, which are volatile and separated from the residue.

Chlorination of high grade concentrate with (chlorine + carbon monoxide + nitrogen) niobium and tantalum
chlorides of very high purity.

Recovery of niobium and manganese from steel slag (Rong, 1994}

 RECOVERY OF METAL VALUES FROM SLAG

4. Cobalt and Copper from Smelter Slag

Selective recovery of cobalt and copper from waste slag requires controlling the quantity of reductant added or
equivalent oxygen partial pressure. When carbon is used as the reductant the amount is found to be about 5 %
of the total slag feed in a laboratory study by Banda and coworkers (2002). These researchers have also found
that the base metal recovery can be significantly improved by certain slag modifiers. The modifiers investigated
are lime (CaO), fluorspar (CaF2) and rutile (TiO2). Rutile has a more selective effect on the recovery of cobalt
than lime and fluorspar, but it leads to lower overall recoveries of cobalt at various levels of addition than in
corresponding cases with fluorspar and lime. The ratio of cobalt recovered to iron recovered increases when
rutile is added, but the increase is not found with lime and fluorspar.

Recovery of niobium and manganese from steel slag (Rong, 1994}

 RECOVERY OF METAL VALUES FROM SLAG
5. Heavy Metals from Zinc Fumer Slag
The tail slag from fuming furnaces still contains about 3 percent
of zinc and some significant quantities of elements such as lead,
indium and germanium.
Crucible Set-up for the Recovery of Metals from Fumer Slag (Zhang et at, 2004)
6. Recovery of Metal Values from Copper and Brass Slag
Recovery of metal or mineral species from copper and brass
smelting slag has been done by one of the three methods,
flotation, leaching and roasting.
- Flotation : copper sulfide minerals and metallic copper
floated and the oxides(Co, Ni) go into the tailings
- Leaching : using leachant (sulfuric acid, hydrochloric acid,
ferric chloride or ammonia) to extract copper
- Roasting: converts the metals in the slag into soluble
sulfate. By adding sulfating agents like sulfuric acid,
ammonium sulfate or ferric sulfate at temperature in the
range 200-600 °C
FLUE DUST and its
treatment
 FLUE DUST
Treatment of the dust from various sources for
resource recovery and to reduce their volume has
led to several innovative developments in recycling.

Summarizes the characteristics and treatment practices associated with the

various steel-making flue dusts.
ELECTRIC ARC FURNACE DUST
• In the production of steel, the major constituents Mean Composition of EAF Dusts (compiled from Lopez et aL, 1993; Keyser, 1981
(marked by superscript a; Little, A. D., 1993; Frenay et aL, 1985}.

of the EAF flue dust generated are iron (24 %),

chromium (10 %), zinc (6 %) and nickel (3 %).
• The particles in EAF dust tend to occur as
aggregates consisting of very fine individual
particles
• The composition of EAF dust varies widely
depending upon the scrap used, the type of
steel being made, the operating conditions and
procedures. (dust from carbon steelmaking are
rich in zinc and lead)
 PROCESSING OPTIONS

The EAF dust treatment processes are grouped in six categories:

1. Thermal : Requiring high temperature treatment of the EAF dust.
2. Recycling : Involving modification of the dust so it can be added to the
furnace.
3. Vitrification : The dust is vitrified into a non-leachable product.
4. Chemical fixation : The dust is encapsulated and made suitable for land fill.
5. Leaching : Zinc is removed from the dust hydrometallurgically
6. Sintering - to produce a compact mass of iron ore that will withstand the
weight of charge when the sinter is placed in a blast furnace.
PYROMETALLURGY PROCESSES
• Most of the industrial methods for the processing
of EAF dust can be considered pyrometallurgical
(the rotary kiln process)
• Three commercially available technologies used to
recycle stainless steel flue dusts are, INMETCO
process, Berzelius Lankstrona, Sweden Plasma
Furnace; and Tetronics/IMS Plasma system.

1. Berzelius, Lankstrona, Sweden Plasma Shaft Furnace
• The process is used to treat hazardous chromium
and nickel-containing stainless steel flue dusts
• The environmental burden appears to be low if
adequate gas-cleaning equipment is used on the
plasma furnace off-gases
2. Tetronics/IMS Plasma System
• When stainless steel flue dusts are being treated,
anthracite is added to reduce the metallic oxides
of chromium, nickel and molybdenum.
• These metals are recovered in the carbon-
saturated "pigs" which are recycled during alloy
steel-making.
3. EAF Dust Treatment by INMETCO Process.
• The wastes are blended with coke or coal in a screw
conveyor.
• Metal oxides are reduced in a rotary hearth furnace. Some
of the carbon in the pellets reacts with oxygen in the
waste to produce metal. A portion of the zinc, lead and
halogens contained in the dust are exhausted into the off
gas treatment system
• Hot metallic sintered pellets are transferred in sealed
containers.
HYDROMETALLURGICAL PROCESSES
The main reason for the development of
hydrometallurgical processes for the treatment of EAF
dust is that a small scale, on-site process could
economic, because of its low capital and operating
costs as well as the potential for the recovery of some
valuable metal-containing products.
1. EZINEX Process 3. Cashman Process
The EAF dust is leached in ammonium chloride solution to Zinc along with lead and cadmium in the EAF dust are pressure
solubilize the zinc, lead and cadmium oxides. Zinc is recovered leached with sulfuric acid in saturated calcium chloride
by electrowinning from the purified solution in the EZINEX solution→ Lead, bismuth and silver are first removed by
process hydrolysis→ Copper is separated by solvent extraction and
recovered by electrowinning→ Cadmium and mercury are
2. Modified Zincex Process recovered by precipitation with zinc dust (cementation).
It consists of leaching, solvent extraction and electrowinning, to
produce 99.99 % purity zinc cathodes or zinc ingots. 4. Caustic Leach Process
Stages: The oxides of zinc and lead and silica are leached in caustic soda
The zinc and cadmium oxides are dissolved in a dilute sulfuric to produce soluble zincate, plumbate and silicate→ silicate is
→precipitation to remove Al and Fe→ Zinc is extracted precipitated by lime→ lead is recovered by cementation→ zinc
selectively by a liquid cationic exchanger→Zinc is electrowon is recovered by electrolysis.
with aluminum cathodes from the loaded electrolyte
 • Some flue dust fines are found to contain
metallic phases, principally nickel and
metal droplets consisting of iron, chromium
and nickel
PHYSICAL • The metallic particles could be separated
from the oxides by gravity separation
SEPARATION • Gravity separation was conducted on a
shaking table
METHOD • Magnetic separation was done with a wet
low intensity magnetic separator (LIMS)
drum
 DIRECT REDUCTION
OF EAF DUST
• It is based on the reduction of the metallic
oxides in the dust by a solid carbon
reductantThe metallic particles could be
separated from the oxides by gravity separation

• Pulverized coal is used as a carbon source and

is intimately mixed with the EAF dust prior to
agglomeration as pellets.

• The reactions occur within the pellets leading

to the formation of iron, zinc, lead and cadmium.

• The zinc, lead and cadmium vapors are Figure 6. . Flow diagram of direct reduction of oxides in EAF dust (Kotraba and
Bottinelli, 1994)
condensed in a splash condenser
 BLAST FURNACE DUST
• The off gases produced in a blast furnace carry dust
containing iron and zinc oxides.
• BF dust contains enough carbon (40-50%) to reduce
the iron content (20-30%) and recover zinc and lead
contents at high enough temperature by feeding
through a hollow electrode from where it passes
through plasma
Recovery Zinc and Magnetite by Jarosite Process
Blast furnace dust produced in steel-making contains
significant percent (10-15) zinc along with iron (often
exceeding 50%) and smaller percentages of lead, manganese
and copper
Stages:
Steel-making baghouse dust is leached with 3 M sulfuric acid
at 80 °C → The filtrate more dust is added and the sulfuric
acid concentration maintained → The leach extract is treated
to produce jarosit → Sodium hydroxide and sodium sulfate
are added, pH maintained at 2 and the mixture heated at 95
°C for 5-8 h → Sodium jarosite formed is filtered and
converted to magnetite → The filtrate after the separation of
sodium jarosite is processed to recover zinc → Residual iron
is precipitated at pH 4 and other metals are removed by
cementation by zinc dust at 60 °C→ electrolysis
 SECONDARY SMELTER DUST
• The dust is generated in the secondary smelting operations
contain volatilizable components such as zinc, lead, cadmium, tin
and alkali chlorides, as well as a variety of entrained particulates
(Fe, Cu, Ca, Si,Al).

Ammonia-Ammonium carbonate circuit to solubilize metal oxides from secondary dust • Some of the values, metals like zinc and copper can be recovered
(Prado and Prado, 1995)

• A hydrometallurgical process, based on the leaching of oxides by

ammoniaammonium carbonate (AAC) aqueous solutions has been
used for the extraction and recovery of zinc, copper and cadmium

Stages:
Copper, zinc, cadmium are are solubilized→ When ammonia is
stripped from the leaching liquor, these metals are rendered insoluble
and precipitate as carbonates → Lead carbonate is dissolved by
ammonium acetate at 80 °C forming lead acetate.

Ammonium acetate circuit for the recovery of lead (Prado and Prado, 1995)
 Flue Dust from Chimney
• Large amounts of zinc ash flue dust containing more than
80 % zinc are accumulated during galvanization processes
at the surface of the molten bath and in the chimney
• Recovery of zinc from a chimney dust by thermal
treatment at 550 °C
• The ammonium chloride improves the recovery efficiency
by minimizing the oxidation of zinc metal
Stages:
1. Ammonium chloride begins to sublime at 340 °C and
equal volumes of ammonia and hydrogen chloride are
evaporated
2. The reaction between the hydrogen chloride and zinc
oxide layer to form molten zinc chloride layer helps
coalescing of zinc droplets to collect together forming
ingots, leading to higher recovery efficiency of zinc.
In-Plant Recycling of Metallurgical Dust
It is called oxyfines and is based on oxyfuel technology
(von Scheele and Johansson, 2002) and it provides an
efficient internal recycling of dust and sludge, which
(the sludge) is recycled without a drying stage. The
particles are agglomerated into solid-state aggregates of
a suitable size, which removes harmful elements
Stages:
The technology uses a special oxyfuel burner to inject the
dust into the furnace→ The sludge is atomized, splitting it into
very small droplets