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Metallurgical Slag
Metallurgical Slag
OF
METALLURGICAL
SLAGS AND DUST
02 Slag Type
04 Incineration Slag
05 Slag Processing
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.
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:
Chemical Composition of Calcium Phosphate Slags from Various Converters (Akbari and
Pickles, 1998)
01 02 03
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.
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.
5. Heavy Metals from Zinc Fumer Slag 6. Recovery of Metal Values from Copper and Brass Slag
The tail slag from fuming furnaces still contains about 3 percent Recovery of metal or mineral species from copper and brass
of zinc and some significant quantities of elements such as lead, smelting slag has been done by one of the three methods,
indium and germanium.
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
Crucible Set-up for the Recovery of Metals from Fumer Slag (Zhang et at, 2004)
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.
1. Berzelius, Lankstrona, Sweden Plasma Shaft Furnace 3. EAF Dust Treatment by INMETCO Process.
• The process is used to treat hazardous chromium • The wastes are blended with coke or coal in a screw
and nickel-containing stainless steel flue dusts conveyor.
• The environmental burden appears to be low if • Metal oxides are reduced in a rotary hearth furnace. Some
adequate gas-cleaning equipment is used on the of the carbon in the pellets reacts with oxygen in the
plasma furnace off-gases waste to produce metal. A portion of the zinc, lead and
2. Tetronics/IMS Plasma System halogens contained in the dust are exhausted into the off
gas treatment system
• When stainless steel flue dusts are being treated,
• Hot metallic sintered pellets are transferred in sealed
anthracite is added to reduce the metallic oxides
containers.
of chromium, nickel and molybdenum.
• These metals are recovered in the carbon-
saturated "pigs" which are recycled during alloy
steel-making.
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
• 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
Recovery Zinc and Magnetite by Jarosite Process
• The off gases produced in a blast furnace carry dust
Blast furnace dust produced in steel-making contains
containing iron and zinc oxides. significant percent (10-15) zinc along with iron (often
exceeding 50%) and smaller percentages of lead, manganese
• BF dust contains enough carbon (40-50%) to reduce and copper
the iron content (20-30%) and recover zinc and lead
contents at high enough temperature by feeding Stages:
through a hollow electrode from where it passes Steel-making baghouse dust is leached with 3 M sulfuric acid
through plasma 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)
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 In-Plant Recycling of Metallurgical Dust
• Large amounts of zinc ash flue dust containing more than It is called oxyfines and is based on oxyfuel technology
80 % zinc are accumulated during galvanization processes (von Scheele and Johansson, 2002) and it provides an
at the surface of the molten bath and in the chimney efficient internal recycling of dust and sludge, which
• Recovery of zinc from a chimney dust by thermal
(the sludge) is recycled without a drying stage. The
treatment at 550 °C
• The ammonium chloride improves the recovery efficiency particles are agglomerated into solid-state aggregates of
by minimizing the oxidation of zinc metal a suitable size, which removes harmful elements
Stages: Stages:
1. Ammonium chloride begins to sublime at 340 °C and The technology uses a special oxyfuel burner to inject the
equal volumes of ammonia and hydrogen chloride are dust into the furnace→ The sludge is atomized, splitting it into
evaporated very small droplets
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.