Unit Processes in Extractive Metallurgy

Kesavan Ravi, Ph.D.

Department of Metallurgical and Materials Engineering,
NITW
Learning objectives

• Discuss basic unit operations of minerals/ores used for metals

extraction

• Apply Ellingham diagrams and basic thermodynamic principles for

extraction of metals

• Summarize unit processes and principles employed in pyro-, hydro-

and electro- metallurgy for mineral beneficiation, refinement and
metal extraction.

• Explain reaction kinetics, heat & material balance and process flow
sheets for the extraction of metals
Text books:

1. Principles of Extractive Metallurgy, H. S. Ray and A. Ghosh, WEL Publishing

2. Mineral Processing, S. K. Jain, CBS Publishing
3. Principles of Extractive Metallurgy, Terkel Rosenqvist, McGraw-Hill Book Company
4. Extractive Metallurgy of Copper, W.G. Davenport, A.K. Biswas, PERGAMON
publishing company
5. Handbook of Extractive Metallurgy: Fathi Habashi; Wiley-VCH

Marks distribution

1. Continuous Evaluation: 20 marks (minor(s)/surprise test/ assignment / quiz)

2. Mid-semester Examination: 30 marks
3. End-semester Examination: 50 marks

Attendance
1. There is no weightage for the attendance
2. But you need to attend 80% of the classes
What is a METAL?

What makes metals special?

Historical Perspective

8000-2000 BC

Stone Age Metal Age

• Earliest known metals to be extracted?

• How did they extract it?
• What came next?
Discovery of metals
• Gold - found uncombined in nature
6000 bc Ancient smelting process: The kiln is lined with
stones and clay the sulfide ore is added. Then
the air is blown into it from goatskin bellows or
• Copper- extracted in an ancient people. The by product (slag) is removed an
copper kiln 4200 bc copper solidifies at the base of the kiln.

It is stronger than copper but has a lower

• Lead- Lead minerals extracted in a
stone furnace 3500 bc
• Bronze- is an alloy( made from
copper and tin) 2500 bc
melting point improving malleability
Calcination and smelting: Calcination is when
the iron ore is heated in the absences of air
causing carbonates to turn into oxides. Smelting
refers to the heating at higher temperatures in a
blast furnace

• Iron- 1500 bc
Aluminium is extracted from the ground in
compounds, it is the purified to aluminium oxide
• Titanium 1719 in the bayer process(this is a process of refining
bauxite to form Aluminium oxide) and then it
undergoes electrolysis in a cryolite solution to
• Aluminium 1825 form aluminium
How and Why did we extract?

• How did extracting a material help humanity?

• Sheer ingenuity of ancient engineers

Chinese Blast furnace, 1130oC Chola Bronze statue of Nataraja

Interesting ways ancient engineers extracted metals
Gold
• Hammered and sheet gold: Cemeteries in Bulgaria in Europe (5th millennium BC)
with accouterments of hammered and sheet gold.

• Gold castings are known from ancient Pharaohnic Egypt, such as the enigmatic face
of the young Pharaoh Tutenkhamen (ca 1300 BC).

• Gold and silver ornaments from the Indian subcontinent are found from Indus Valley
sites such as Mohenjodaro (ca 3000 BC).

Some of the methods

• Panning alluvial sands from placer deposits.

• ‘Gold-digging ants’ (marmot), a type of rodent found in Afghanistan, who dig up the
river sand which could then have been panned for gold by the inhabitants.

• Granulation of gold: Ancient Greeks (600 BC). Surface tension was used to turn
melted gold filings into spheres. The granulation technique was also used to make
gold jewelry in India in the late 1st millennium BC to early Christian era.
Interesting ways ancient engineers extracted metals
Zinc

• The earliest firm evidence for the production of metallic zinc is from India.

• Semi-industrial production of metallic zinc at the Zawar area of Rajasthan.

• The Rasaratnakara, a text ascribed to the Indian scientist Nagarjuna, of the early
Christian era describes this method of production of zinc.

Some of the methods

• Downward distillation of the zinc vapour formed after smelting zinc ore using
specifically designed retorts with condensers and furnaces, so that the smelted
zinc vapour could be drastically cooled down to get a melt that could solidify to
zinc metal.
Interesting ways ancient engineers extracted metals
Iron
• Iron in native metal state as meteoric iron: North American Indians to make
weapons.
• The Hittite kingdom (~2nd millennium BC) was one of the major early iron
producing centers and was thought to have a monopoly of iron production, and
iron production
• Iron in India possibly from the late second millennium BC
• The earliest large forging is the famous iron pillar at New Delhi dated by inscription
to the Gupta period of the 3rd c. AD – Also corrosion free!

Some of the methods

• Iron has a high melting point of around

1550oC it was commonly produced in the
Old World by reducing the ore to metal in
the solid state to produce bloomery iron
which was then wrought to give low carbon Simple bloomery and bellows
wrought iron (0.1-0.2 % C).
• Cast iron was produced in China prior to other parts of the world in small blast
furnaces which were precursors to the modern blast furnaces.
Interesting ways ancient engineers extracted metals
Copper

• Native copper: First metal used by man in ancient Turkey and Mesopotamia (7th
millennium BC).

• Early copper artifacts (6th millennium BC): Pre-Indus Valley sites of Baluchistan.

• Ancient mining of copper ores from the Khetri region of Rajasthan in northwestern
India (3rd-2nd millennium BC).

Some of the methods

• Native copper is abundantly available in large masses in the Great Lakes region
of North America and was used fairly extensively by the North American Indians to
make weapons and implements solely by hammering and annealing so that
casting and smelting was not attempted.

• Clear early evidence for smelting copper comes from the Middle East from about
the fourth to third millennium BC onwards, from parts of Israel, Jordan and Egypt
where copper oxide ores such as green malachite were smelted at temperatures
of around 1200oC.
World Metal Production

1800 Million tonnes/yr!!

Tripled since 95!!
What is Extractive Metallurgy ?

Study and understanding for:

Naturally existing ore/minerals à (extraction of metals) à (refine) à Metals

Naturally occurring Minerals : Inorganic compounds with non-metals like S,O,N

etc.

Hematite (Fe2O3), Magnetite (Fe3O4), Chalcopyrite (CuFeS2), Dolomite

(CaCO3.MgCO3) etc etc.

Sources

Earth Crust (Aluminum: 8.1%, Iron 5.1%, Calcium: 3.6%, Sodium: 2.8%,
Potassium: 2.6%, Magnesium: 2.1%, Titanium: 2.1%, Manganese:
0.10%)

Ocean water: ( Na: 10500 g/ton, Mg: 1270 g/ton, Ca: 400 g/ton, K: 380
g/ton) ; Ocean nodules (Mn: 23.86%, Mg 1.66%, Al 2.86%, Fe 13.80%..)

Recycled scrap (at the end of metals’ life)

Why do you need Extractive Metallurgy?

• To extract metals with desired properties

• To understand what is valuable in an ore

• To advance the humanity’s ever increasing needs

• To minimize energy requirements and impact on environment

Minerals
• A mineral is a chemical compund of organic or inorganic origin with definite
chemical and physical properties.
• The International Mineralogical Association (IMA) recognizes 5,413 official
mineral species

Minerals

Non-Metallic
Metallic

Fuel Minerals Other non-

Ferrous Non-Ferrous metallics
Iron, Manganese etc Copper, Bauxite etc Coal, Petroleum,
Natural gas etc. Mica, Limestone,
graphite etc.
Types of metals extracted

Rudyard Kipling:
“Gold for the mistress, Silver for the maid, Copper for the craftsman, Cunning
at his trade. ‘Good’, said the Baron, Sitting in his hall, ‘But iron-cold iron’ is
master of them all.”

• Ferrous metals: 90 percent of all metals, used today are iron and steel – largely
structural, automotive, marine etc à Can be considered as basis for civilization!

• Non-ferrous metals:
• Airplanes and the spacecraft’s (Ti, Al) à light and strong
• Electrical applications (Cu, Ag): Superb conductor of electricity
• Catalysts (Au, Pt, Pd)
Mineral Map: World Good Source (interactive website):
https://mrdata.usgs.gov/major-deposits/map-
us.html

Australia, Canada: uranium ores, Gold (Oceans too!!)

Mexico: Silver
China, Brazil, Australia, Russia and India: Iron ore (70% of
the world's iron ore production)
Australia, Brazil, Guinea, Guyana, India, Jamaica, Russia,
Suriname, United States and Venezuela: Bauxite
Mineral Map: India

• Abundant: Al, Be, Cr, Fe, Mn,

Mg, Ti, Zr, Th, Pb and Zn, raw
earth metals

• Scarce: Co, Ni, Cu, Sn, Au, V,

Ni, Cd and U.

• Poor or not found: Sb, Bi, Co,

Hg, Mo, Nb, Ta, Sr, Se, Ag, W,
Pt

Good Source (interactive website):

https://mrdata.usgs.gov/major-deposits/map-
us.html
What are ores

• Naturally occurring Rock/Sediment from which important elements can be

extracted
• Concentration of elements in the ore is very important!
• Are the terms minerals ßà ores interchangeable?
• Seldom pure minerals

Ores à Mixture of minerals + Impurities (Gangue)

Manganese ore Lead ore Gold ore

(Ba,H2O)2Mn5O10 PbSO4
Types of ores

• Oxide ores: Examples: Fe2O3, Fe3O4

Apart from Fe, other heavy metals which are produced from oxide ores are:
Manganese, Chromium, Titanium, Tungsten, Uranium and Tin.

• Sulphide ores: Copper ore (CuFeS2, Chalcopyrite), sphalerite (Zn, Fe)S,

Galena PbS, Pyrite FeS2.
Others: Nickel, Zinc, Mercury and Molybdenum

• Halide ores: Rock salts of Sodium, Magnesium chloride in sea water

Commercial production of metals

• Availability of ore deposits

• Concentration of metal in the ore

• Availability of technology of extraction and refining of that metal

• Physical and chemical properties of the metal

• Market demand of that metal

Economy of the process

• Readily available,
• Easily produced
• Available at low processing cost
• Desired properties
Unit processes and Unit operations

• Any metal extraction process is the combination of similar and

unique kind of steps known as Unit processes/unit operations.

• Unit operations: Physical operations like crushing, grinding, sizing,

mixing through agitation, filteration, distillation, comminution

• Unit processes: Chemical processes like leaching, smelting,

roasting, Electrolysis, decarburization, Dephosphorization,
Degassing, Deoxidation etc.

Combination of all unit steps/processes are resulting in

Flow-Sheets
Flow sheet Cu extraction process

Unit operations
• Crushing, Grinding, Floatation

Unit processes

• Roasting, smelting, Blowing,

Refining, Electrolysis are
Unit processes
Flow sheet iron and steel extraction process
Flow sheet Zinc extraction process
Different reactor designs

a) Fixed bed reactor b) Shaft furnace c) Fluidized bed d) Retort e) Rotary

kiln f) Reverberatory furnace g) Electric arc furnace
Classification of unit processes

Classification according to chemical reactions:

• Oxidation: Roasting, sintering

• Reduction: Blast furnace ironmaking

• Chlorination: Titanium (converting to tetrachloride)

• Electrolytic reduction: Zinc and Aluminum production

• Electrolyte refining: Refining of Copper and Nickel

Classification of unit processes

Classification based upon methods of metal extraction

• Physical separation/Mineral processing

The objective is to concentrate the metallic content in the ore, achieved
by a series of comminution (crushing and grinding), screening and
separation process

• Pyrometallurgy
It involves the smelting, converting and refining of metal concentrate.

• Hydrometallurgy
It involves the precipitation of metal in an aqueous solution.

• Electrometallurgy
Electrolysis process to extract metal. Electrowinning: Extraction of the
metal from electrolyte; Electrorefining: Refining of impure metals in
the form of an anode.
Principles you must know ?

• Heat and mass balance : to know the material requirement

• Thermodynamics : Feasibility criteria

• Kinetics and rate of process: How long it take to complete the process

• Heat transfer: For improving the thermal efficiency of the process

• Fluid dynamics: To know the mixing of the reactor

• High temperature properties of metals/slag: To know the physical properties of

various phases, their mobility and role in metal refining processes.

• Electrochemistry: To estimate, overpotential, current efficiency