CHEMICAL TECHNOLOGY11

– ECP 429
Madzokere T C
 TOPICS

 1.RUBBER TECHNOLOGY
 2.CEMENT MANUFACTURING
 3. CERAMIC TECHNOLOGY
 4.INDUTSRIAl TRENDS AND APPLICATIONS OF
NANOTECHNOLOGY IN CHEMICAL PROCESS INDUSTRIES
 5.MINERAL PROCESSING
 6.COAL TECHNOLOGY
 1. RUBBER
TECHNOLOGY
 Rubber Technology
 HISTORICAL BACK GROUND

 The name rubber was given by Priestly,(the

discoverer of oxygen) who first observed
its ability to ‘rub out’ a pencil mark.

 Columbus found the natives of the West

Indies playing games with rubber balls.
World War 11 - Japanese’s invasion of the
United States

Natural rubber supplies were shut off

Stimulated the building up of the synthetic

rubber plant.
•Rubber – a product of the Americas, but
achieved its greatest growth by transplantation
to the Far East.

•Extensive research during the 1930s period

led to the discovery of the emulsion
copolymerization of butadiene and styrene,
and of butadiene and acrylonitrile
HISTORY MAKERS

•J.B Dunlop
•T. Hankook
•T. Michellin
•C. Macintosh
•M Goodyear
Natural Rubber (NR)

•Harvested from the latex producing tree

Hevea Brasiliensis, a native of South America

•Natural rubber plantations –

Malaya, Indonesia, Liberia, etc

Areas free from pests and fungus diseases.

•Trees require ~ 7 years to reach bearing age

•The collection and processing of the latex

requires considerable labour.

•Latex is obtained by tapping the tree

•Collected frequently in small cups

Chemical Name of the rubber
content - cis-1,4,- poly isoprene

Chemical Structure - ???

Harvesting Latex
•COMPOSITION AND PROPERTIES OF RUBBER
LATEX

Milky liquid - colloidal solution of rubber

particles in water

The particle diameters range between 0.05 µ

and 5 µ.

Freshly tapped has a pH of 6.5 to 7.1 and

density 0.98 g/cm3
The total solids of fresh field latex vary
typically from 30 to 40 wt %

The solid phase typically contains:

• 96% rubber hydrocarbon,

• 1 wt % protein

• 3 wt % lipids

• traces of metal salts.

Read on stabilization, concentration and
processing of latex

Uses of NR -

Read on properties of Natural Rubber

SYNTHETIC RUBBER

Classified as :

•Vulcanizable and non-vulcanizable

•Chemical composition of the polymer

Polymerization Techniques

 Bulk,
Solution,
 Suspension
 Emulsion polymerization
SYNTHETIC RUBBER POLYMERIZATION

•The various methods of production of

synthetic rubbers have MUCH IN COMMON

•Monomers are not particularly difficult to

handle at reasonable pressures.

•Dissipation of heat of polymerization is

frequently the controlling consideration.
•Control of molecular weight and of molecular
configuration have become the predominant
quality considerations.

•The rubber quality and rate of reaction both

fall as polymerization proceeds.

•It is customary to stop the reaction short of

complete conversion to rubber.
•Recovery of the unreacted monomers and
purification is an essential step in economical
synthetic rubber production.

• Monomer Recovery Methods – steam

stripping or distillation.

•Water /solvent is removed by a combination

of mechanical squeezing and by passage
through a vacuum section.
•Precipitating the rubber from the latex
emulsion or from the solvent in crumb form

•Water /solvent is removal - a combination of

mechanical squeezing and by passage through
a vacuum section.

•Drying
•NB: Rubber is a difficult material to dry and
care must be taken not to overheat it or
otherwise cause its deterioration.

•Drying time in conventional hot air apron

driers may be as long as several hours
MANUFACTURE OF STYRENE BUTADIENE
RUBBER ( SBR )

SBR – Copolymer of styrene that contains over

50% butadiene.

NB: For a copolymer with >50% Styrene the

polymer becomes increasingly plastic and is
used in latex paint.
•Monomer ratio –

[70-75% Butadiene] to [30 – 25%]

Styrene

Polymerization technique

• Hot

•Cold
Polymerization temp : 5°C

Residence Time : 8 to 12 Hours

Heat of polymerization : 1280 kj/kg rubber

Mr regulation(modifier) : C12 mercaptan

Conversion : 60 -75 %
•Un reacted butadiene is recovered by flashing
off & Styrene by steam distillation

NB the emulsion is infect a latex

•Latex is coagulated , washed and dewatered

prior to drying
- 60 -75 %
Properties of SBR

High abrasion resistance

High fatigue resistance
Low heat build up
High resilience
Uses
• 70% used for tire and tread industry
•15% for mechanical goods
•10% sold as latex
Typical Recipe for Cold Emulsion SBR

Parts by Function
Weight
Butadiene 72 Monome
r
Styrene 28 Monome
r
d-isopropyl 0.08 Catalyst
benzene
hydrperoxid
e
Ferrous 0.14 Activator
sulphate
Dodecyl modifier Modifier
mercaptan
Potassium 0.18 Buffer
pyrophaosp
hate
Rosin acid 4.0 Emulsifie
soap
r
Water 180
NITRILE RUBBER (NBR)

•Polymerisation technique – Emulsion

•Copolymer of butadiene and acrylonitrile

•Acrylonitrile content may be varied from 20 –

50% depending on the properties desired.

•Resistance to hydrocarbons and gas

permeation increases with increasing nitrile
content
NBRs are resistant to :

 oils, solvents, water salts, aliphatic

compounds.

They are serviceable for continuous use up to

120°C in air and 150°C immersed in oil.
Neoprene/ CR

Polymer of 2-chloro-1,3 butadiene

Polymerization technique – Emulsion

Resistant to oxidation, and heat (Flame

resistant)

Uses – automobile parts, adhesives, sealants,

coatings
•Expensive rubber and is only used where its
special properties are needed.

•Decreasing the nitrile content present

increases the low temperature properties and
resilience
Butyl Rubber
Copolymer of isobutylene with about 2%
isoprene.

Isoprene imparts sufficient unsaturation to the

molecule to permit curing or vulcanization

Properties – low permeability to gases

Inert to oxidation

Uses – making tire tubes and the linings if

tubeless tires.
RUBBER TECHNOLOGY
 Purerubber ( Natural or Synthetic)
is not for use on its own

 Desired
properties are achieved
through the art of rubber
compounding
RUBBER TECHNOLOGY
Desired Properties:
 Plasticity
 Elasticity
 Toughness
 Hardness or Softness
 Abrasion resistance
 Impermeability
 RUBBER TECHNOLOGY
 Rubber Compounding chemicals
are divided into groups according
to their uses
1. Vulcanizing agents – usually
sulphur compounds which react
with the polymer to produce a
cross linked material.
Rubber Technology
2. Accelerators – reduce the time
required for the vulcanization of
rubber from several hours to a few
minutes
3. Age resistors or antioxidants or anti
–flex cracking agent – protect rubber
goods from attack by oxygen and
ozone in the atmosphere
Rubber Technology
4. Catalytic Plasticizers or Peptizers –

 Reduce the viscosity of the rubber

to permit easier processing.

 Important in reclaiming vulcanized

rubber and in softening high
molecular weight crudes
RUBBER TECHNOLOGY
5. Fillers –

 to harden or dilute the mix

 Enhance reinforcement of the mix

 To cheapen the product

RUBBER TECHNOLGY
6. Softeners or extenders - ??
 2:CEMENT
MANUFACTURING
MANUFACTURE OF CEMENT
Historical Background
 Cement dates back to Antiquity

 The Greeks and Romans used volcanic

tuff mixed with lime for cement and a
number of these structures are still
standing.
MANUFACTURE OF CEMENT
 The credit for its discovery is given to the
Romans, who mixed lime (CaCO3) with volcanic
ash, producing a cement mortar which was
used during the construction of such
impressive structures as the Colosseum.

 When the Roman empire fell, the information

on how to make cement was lost and was not
rediscovered until the 16th century.
MANUFACTURE OF CEMENT
 Egyptians used cement to construct pyramids
MANUFACTURE OF CEMENT
 In 1824 an Englishman, Joseph Aspdin,
patented artificial cement made by the
calcinations of an argillaceous limestone.

 He called this ‘Portland’ because concrete

made from it resembled a famous building
stone obtained from the Isle of Portland near
England
MANUFACTURE OF CEMENT
 Manufacturing procedure

 Two types of materials are necessary for

the production of Portland cement:
 Calcium rich (calcareous) material e. g

limestone, chalk etc.

 Silica rich (argillaceous) material e. g

clay.
MANUFACTURE OF CEMENT
 In addition to natural materials some plants
use blast – furnace slag (NEW ZIM STEEL) and
precipitated calcium carbonate obtained as a
by-product in the alkali and synthetic
ammonium sulphate industry.

 Sand, waste bauxite, and iron ore are

sometimes used in small amounts to adjust
the composition of the mix.
MANUFACTURE OF CEMENT
 Gypsum (usually 4 -5 %) is added to
regulate the setting time of cement.

 Cement clinker is manufactured by both

wet and dry processes (how do they
differ?).
MANUFACTURE OF CEMENT
 Mining of major raw materials

 Limestoneis mined (where in Zimbabwe?)

transported to the factory.

 Crushing

 Thematerial is crushed to a maximum size of about

 100mm in diameter.
MANUFACTURE OF CEMENT
 Material is continuously sampled to
determine the quantity of the various
additives, such as iron oxide, alumina,
silica required to make the ideal
chemical composition.
MANUFACTURE OF CEMENT
 Pre -homoginization

 Initial blending occurs in the prehomoginization stage

 Raw material grinding

 The blended raw materials and final additives are

introduced to a ball mill or vertical roller mill where
they are dried and ground into fine powder, known as
kiln feed.
MANUFACTURE OF CEMENT
 Pre-heater

 The kiln feed is introduced into the cyclone

pre heater, which uses kiln exit gases to heat
the material to approximately 800°C.
MANUFACTURE OF CEMENT
 Rotary Kiln

 Thepreheated material enters the rotary kiln and is burned

using flame and temperature goes up to about 1450°C.

 Thetendency in recent years has been to lengthen the

rotary kiln in order to increase its thermal efficiency.

 Dryprocess kilns may be as short as 45 m , but in the wet

process 90 – 180 m kilns are not uncommon and the
internal diameter is usually 2.5 to 6 m.
MANUFACTURE OF CEMENT
 The kilns are rotated at 0.5 – 2 rpm depending
on size and are slightly inclined, so that
material fed in at the upper end travel slowly
to the lower firing end, taking from 1 – 3 hours.

 The kiln has to withstand severe abrasions and

chemical attack at high temperatures good
refractory materials such as high alumina and
high magnesia bricks are widely used.
MANUFACTURE OF CEMENT
 Thematerial discharged from the kiln,
(known as clinker consists of granular
masses from 3 – 20mm in size) is
channeled to the clinker cooler.

 Computers are now used to improve

kiln control.
 Keys to Combustion Efficiency
 “The kiln is the heart of the cement plant. The

more efficient the combustion process, the

more heat that is unlocked, the less fuel that
is wasted, and the less ash that is produce.”
  
 Here are a few basic things to consider in this

intricate balance.
MANUFACTURE OF CEMENT
Right Fuel Particle Size

 Thekey to burning any fuel is to make sure

that the particles are small enough that
they can be burned quickly and easily.

 Producingsmaller particle sizes requires

using more grinding energy.
MANUFACTURE OF CEMENT
 The balance then becomes a trade-off
between how fine to grind and how much
more efficient the combustion process
becomes with a finer grind.

 Since a smaller particle size means the fuel

burns quicker and easier, it also means there
are more safety concerns with handling,
conveyance and storage.
MANUFACTURE OF CEMENT
Source of heat

 Theactual combustion process is an incredibly

complex series of chemical reactions that start off
with fuel, air, and an ignition source.

 In
fact, there are actually more than one thousand
separate reactions involved from the transition of
fuel into the final combustion products of carbon
dioxide and water.
MANUFACTURE OF CEMENT
 The kindling temperature for bituminous coal
is roughly 300° C while the kindling
temperature for petcoke is about 700° C.
(Petcoke has a higher kindling temperature
because as it is almost pure carbon and has
very few volatiles compared to coal.)

 Thecombustion process continues provided

there is enough fuel and air supplied.
MANUFACTURE OF CEMENT
 Effective mixing of air and fuel

“Operators usually don’t have much ability to

impact the mixing process except to make
sure that the amount of primary air is
consistently supplied”.
 The actual physical mixing then becomes a

function of burner design and flame

geometry.
MANUFACTURE OF CEMENT
 Fuel that isn’t burned within the flame poses
a critical safety concern because of its
potential to accumulate and combust farther
on down the kiln.

 Insufficient
primary air can also cause
accumulations of solid fuel in the burner pipe
system with potentially disastrous results.
MANUFACTURE OF CEMENT
Maintenance of a stable secondary air temperature

The combustion process heats up unburned fuel,

feed, coating, refractory, and the gases inside the
kiln. “That’s why it’s so important to maintain
stable secondary air temperature”.

That can only be accomplished by maintaining

consistent clinker cooler performance.
MANUFACTURE OF CEMENT
Flame stability.

 Optimalflame length can promote rapid

heating and cooling of the clinker.

 Flame stability also means reduced back end

temperatures which in turn means lower heat
losses from exit gases and shell radiation.
MANUFACTURE OF CEMENT
 The right flame length also optimizes the
ID fan capability and reduces the
potential for NOx formation.

 Unstable flames on the other hand means

a varying ignition point, a variable stand
off distance from the burner tip, high risk
of flame out, and potential explosion risk.
 Limiting NOx , Sox and CO formation
 Thermal NOx is also generated in and around
the flame at temperatures greater than 1200°
C.
  
 A short hot burning zone can reduce the

formation of thermal NOx.

MANUFACTURE OF CEMENT
 SO is formed as sulfide or elemental sulfur is
2
oxidized at temperatures of 300 to 600° C. Limiting
the source of sulfur or the necessary oxygen can limit
the potential for SO2 formation.

 Carbon monoxide formation is another concern. CO

is either formed because of incomplete combustion
or the rapid cooling of combustion products below
the ignition temperature of CO (610° C). Either
situation is detrimental to optimizing the process.
MANUFACTURE OF CEMENT
 Optimizing the combustion process is
the key to optimizing kiln operations
MANUFACTURE OF CEMENT
Clinker Cooler and Storage

 The clinker is discharged from the kiln

into air quenching coolers, which quickly
brings down the temperature to ≈ 100 –
200 °C. These coolers simultaneously
preheat the combustion air.

 The clinker is stored in silos.

MANUFACTURE OF CEMENT
Cement Grinding

 The cement is ground into fine powder in a ball

mill along with additives, e.g. gypsum or slag

 The percentage of these additives and fineness

of the final product determines the grade of
cement.
Environmental protection and
pollution control in cement
manufacturing
 Home work
4. CERAMICS
TECHNOLOGY
Applications and Processing of
Ceramics
ISSUES TO ADDRESS...
• How do we classify ceramics?

• What are some applications of ceramics?

• How is processing of ceramics different from metals?

73
Classification of Ceramics
Ceramic Materials

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics
-optical -whiteware -bricks for -sandpaper -composites -engine
-composite -structural high T -cutting -structural rotors
reinforce (furnaces) -polishing valves
-containers/ Adapted from Fig. 13.1 and discussion in
bearings
household Section 13.2-8, Callister & Rethwisch 8e. -sensors

74
Ceramics Application: Die Blanks
• Die blanks: die Ad
-- Need wear resistant properties! Ao tensile
force
die
• Die surface: Adapted from Fig. 11.8(d),
Callister & Rethwisch 8e.
-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.

Courtesy Martin Deakins, GE

Superabrasives, Worthington,
OH. Used with permission.

75
Ceramics Application:
Cutting Tools
• Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

• Materials: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds Single crystal
diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
polycrystalline
resharpen by microfracturing diamonds in a resin
along cleavage planes. matrix.
Photos courtesy Martin Deakins,
GE Superabrasives, Worthington,
OH. Used with permission.

76
Ceramics Application: Sensors
• Example: ZrO2 as an oxygen sensor
Ca 2+
• Principle: Increase diffusion rate of oxygen
to produce rapid response of sensor signal to
change in oxygen concentration
• Approach: A substituting Ca2+ ion
Add Ca impurity to ZrO2: removes a Zr 4+ ion and
an O2- ion.
-- increases O2- vacancies
-- increases O2- diffusion rate
• Operation:
sensor
-- voltage difference produced when
gas with an reference
O2- ions diffuse from the external unknown, higher gas at fixed
oxygen content O2-
surface through the sensor to the diffusion
oxygen content
reference gas surface.
-- magnitude of voltage difference
 partial pressure of oxygen at the + -
voltage difference produced!
external surface
77
Refractories
• Materials to be used at high temperatures (e.g., in
high temperature furnaces).
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• Silica refractories - silica rich - small additions of alumina
depress melting temperature (phase diagram):
2200 3Al2O3-2SiO2
T(ºC)
mullite
2000 Liquid
(L) alumina + L

1800
crystobalite mullite alumina
+L +L +
Fig. 12.27, Callister &
Rethwisch 8e. (Fig. 12.27
1600 mullite adapted from F.J. Klug and
mullite R.H. Doremus, J. Am. Cer.
Soc. 70(10), p. 758, 1987.)
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)
78
Advanced Ceramics:
Materials for Automobile Engines
 Advantages: • Disadvantages:
◦ Operate at high – Ceramic materials are
temperatures – high brittle
efficiencies – Difficult to remove internal
◦ Low frictional losses voids (that weaken
◦ Operate without a structures)
cooling system – Ceramic parts are difficult
◦ Lower weights than to form and machine
current engines

• Potential candidate materials: Si3N4, SiC, & ZrO2

• Possible engine parts: engine block & piston coatings

79
Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet

Properties/Materials:
-- Facing plates -- hard and brittle
— fracture high-velocity projectile
— Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile
— deform and absorb remaining energy
— aluminum, synthetic fiber laminates

80
 Ceramic Fabrication Methods (i)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Blowing of Glass Bottles: • Pressing: plates, cheap glasses
Pressing -- glass formed by application of
Gob
operation
pressure
Parison
-- mold is steel with graphite
mold lining
• Fiber drawing:
Compressed
air

Suspended
parison

Finishing
mold wind up
Adapted from Fig. 13.8, Callister & Rethwisch 8e. (Fig. 13.8 is adapted from C.J.
Phillips, Glass: The Miracle Maker, Pittman Publishing Ltd., London.) 81
Sheet Glass Forming
 Sheet forming – continuous casting
◦ sheets are formed by floating the molten glass on a pool of
molten tin

Adapted from Fig. 13.9,

Callister & Rethwisch 8e.

82
Glass Structure
• Basic Unit: Glass is noncrystalline (amorphous)
4- • Fused silica is SiO2 to which no
Si0 4 tetrahedron
impurities have been added
Si 4+ • Other common glasses contain
O2- impurity ions such as Na+, Ca2+,
Al3+, and B3+

• Quartz is crystalline
Na +
SiO2: Si 4+
O2-

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.

83
Glass Properties
• Specific volume (1/r) vs Temperature (T):
• Crystalline materials:
Specific volume
-- crystallize at melting temp, Tm
-- have abrupt change in spec.
Supercooled Liquid
Liquid (disordered) vol. at Tm

Glass • Glasses:
(amorphous solid)
-- do not crystallize
Crystalline -- change in slope in spec. vol. curve at
(i.e., ordered) solid

Tg Tm T glass transition temperature, Tg

Adapted from Fig. 13.6, -- transparent - no grain boundaries to
Callister & Rethwisch 8e.

scatter light
84
Glass Properties: Viscosity
• Viscosity, h:
-- relates shear stress () and velocity gradient (dv/dy):

t
dy dv 
glass dv 
dy dv / dy
t
velocity gradient

h has units of (Pa-s)

85
Log Glass Viscosity vs. Temperature
• soda-lime glass: 70% SiO2
• Viscosity decreases with T
balance Na2O (soda) & CaO (lime)
• borosilicate (Pyrex):
fu 13% B2O3, 3.5% Na2O, 2.5% Al2O3
96 yre e

• Vycor: 96% SiO2, 4% B2O3

so ss

se ilic
gla

%
da

ds a
P

• fused silica: > 99.5 wt% SiO2

s
-lim

ilic

10 14
Viscosity [Pa-s]

strain point
a

annealing point
10 10

10 6 Working range:
glass-forming carried out
10 2
Tmelt Adapted from Fig. 13.7, Callister & Rethwisch
8e. (Fig. 13.7 is from E.B. Shand,
1 Engineering Glass, Modern Materials, Vol. 6,
200 600 1000 1400 1800 T(ºC) Academic Press, New York, 1968, p. 262.)

86
Heat Treating Glass
• Annealing:
-- removes internal stresses caused by uneven cooling.
• Tempering:
-- puts surface of glass part into compression
-- suppresses growth of cracks from surface scratches.
-- sequence:
before cooling initial cooling at room temp.
cooler compression
hot hot tension
cooler compression

-- Result: surface crack growth is suppressed.

87
• Ceramic Fabrication
techniques:

-- glass forming (pressing,

blowing, fiber drawing).

-- particulate forming
(hydroplastic forming, slip
casting, powder pressing, tape
casting)

-- cementation
88
Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Hydroplastic forming:
• Mill (grind) and screen constituents: desired particle size
• Extrude this mass (e.g., into a brick)

Ao
container die holder
force Adapted from
ram billet extrusion Ad Fig. 12.8(c),
Callister &
container die Rethwisch 8e.

• Dry and fire the formed piece

89
Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Slip casting:
• Mill (grind) and screen constituents: desired particle size
• Mix with water and other constituents to form slip
• Slip casting operation
pour slip absorb water pour slip drain “green
into mold into mold into mold mold ceramic” Adapted from Fig.
“green 13.12, Callister &
ceramic” Rethwisch 8e. (Fig.
13.12 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)
solid component hollow component

• Dry and fire the cast piece

90
Typical Porcelain Composition
(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp.
glass

91
 Hydroplasticity of Clay
• Clay is inexpensive Shear
• When water is added to clay
-- water molecules fit in between
layered sheets charge
-- reduces degree of van der Waals neutral
bonding
-- when external forces applied – clay
particles free to move past one
weak van
another – becomes hydroplastic
der Waals
• Structure of bonding
4+
Kaolinite Clay: charge Si
3+
Adapted from Fig. 12.14, Callister & neutral Al
-
Rethwisch 8e. (Fig. 12.14 is adapted from
W.E. Hauth, "Crystal Chemistry of
OH
2-
Ceramics", American Ceramic Society
Bulletin, Vol. 30 (4), 1951, p. 140.)
O

Shear 92
 Drying and Firing
• Drying: as water is removed - interparticle spacings decrease
– shrinkage .
Adapted from Fig.
13.13, Callister &
Rethwisch 8e. (Fig.
13.13 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet body partially dry completely dry

Drying too fast causes sample to warp or crack due to non-uniform shrinkage

micrograph of porcelain
Si02 particle
• Firing: (quartz)
-- heat treatment between glass formed
900-1400ºC around
the particle
-- vitrification: liquid glass forms
from clay and flux – flows
between SiO2 particles. (Flux 70 mm
Adapted from Fig. 13.14, Callister & Rethwisch 8e.
lowers melting temperature). (Fig. 13.14 is courtesy H.G. Brinkies, Swinburne
University of Technology, Hawthorn Campus,
Hawthorn, Victoria, Australia.)
93
Ceramic Fabrication Methods (iib)

GLASS PARTICULATE CEMENTATION

FORMING FORMING

Powder Pressing: used for both clay and non-clay compositions.

• Powder (plus binder) compacted by pressure in a mold

-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat (

94
Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,

Callister & Rethwisch 8e.
Aluminum oxide powder:
-- sintered at 1700ºC Adapted from Fig. 13.17, Callister
for 6 minutes. & Rethwisch 8e. (Fig. 13.17 is from
W.D. Kingery, H.K. Bowen, and
D.R. Uhlmann, Introduction to
Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.)

15 m
95
Tape Casting
 Thin sheets of green ceramic cast as flexible tape
 Used for integrated circuits and capacitors
 Slip = suspended ceramic particles + organic liquid

(contains binders, plasticizers)

Fig. 13.18, Callister &

Rethwisch 8e.
96
Ceramic Fabrication Methods (iii)
GLASS PARTICULATE CEMENTATION
FORMING FORMING
• Hardening of a paste – paste formed by mixing cement

material with water

• Formation of rigid structures having varied and complex
shapes
• Hardening process – hydration (complex chemical
reactionscement
• Portland involving water and cement
– production of: particles)
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400ºC)
-- grind into fine powder

97
Summary
• Categories of ceramics:
-- glasses -- clay products
-- refractories -- cements
-- advanced ceramics
• Ceramic Fabrication techniques:
-- glass forming (pressing, blowing, fiber drawing).
-- particulate forming (hydroplastic forming, slip casting,
powder pressing, tape casting)
-- cementation
• Heat treating procedures
-- glasses—annealing, tempering
-- particulate formed pieces—drying, firing (sintering)

98
5. MINERAL PROCESSING
TECHNOLOGY
Mineral Processing Overview
 Mineral Processing Terminology,
Economics
 Comminution and Classification
 Physical processing methods
 Chemical processing methods
 Waste products

treatment and
disposal
 Process plant

flow sheets:
 Importance of Mineral Processing

“No substance has been as important as metal in the

story of man's control of his environment.
Advances in agriculture, warfare, transport, even
cookery are impossible without metal. So is the
entire Industrial Revolution, from steam to
electricity.”

Read more:
http://www.historyworld.net/wrldhis/PlainTextHist
ories.asp?historyid=ab16#ixzz13XSEyvNz
 Importance of Mineral Processing

Bronze Age- Bronze is in use

in Sumer, at Ur, in around
2800 BC

Iron Age - from the 11th century BC

onwards, steel replaces bronze
weapons. It becomes essential
from now on, to have a good stee
blade rather than a soft and
indifferent one
Mineral Processing Overview:

 Geology-Mining-Processing Relationship

 Mineral Processing Terms

◦ Definitions

 Mineral Economics review

 Project Stages
 Comminution & classification circuits
 Comminution Methods
◦ Principles
◦ Crushing
◦ Grinding

 Classification Methods
◦ Principles
◦ Hydrocyclone
◦ Screening
 Physical Processing Methods
◦ Gravity
◦ Magnetic
◦ Electrostatic
◦ Radiometric
◦ Froth Flotation
◦ Solid/liquid separation
 Chemical Processing
◦ Basic Circuits
◦ Leaching
◦ Solvent Extraction
◦ Precipitation
◦ Drying

 Downstream – Purified
Product
◦ Electrowinning
◦ Smelting
Waste Stream Management:

 Tailings Disposal
◦ Surface
◦ Underground

 Effluent Treatment
◦ Chemical Precipitation
◦ Membrane Technology
 Geology – Mining – Processing

•All 3 aspects must be favorable to make a

deposit economically viable

• Geology: Find it. Is it big enough to be

economic?
•Mining: Dig it. Is it economically
recoverable from the ground?
•Processing: Extract it. Is it economically
separable from the host rock?
 Prevalence of mineral processing
 Mining is all around us!
 In Zimbabwe there are : ??????????
◦ Coal plants
◦ Industrial minerals (limestone)
◦ Nickel/cobalt metallurgical complex
◦ Many copper/zinc mines and mills,
◦ Nickel mines
◦ Operating diamond mines
◦ Gold mines
Introduction to Mineral Processing

 Scope of mineral
processing

 Definitions

 Economics

 Project Stages
 Mining Terminology - Review
Miners send their products to their customer – the mill.
 Ore : Rock that contains a mineral or minerals in sufficient quantities as to
make commercial extraction (mining – milling) profitable.
 Grade : A measure of concentration of a mineral/metal contained in rock
(or ore). Gold and other precious metals – g/t or oz/t, base metals - %,
uranium – kg/tonne, rare earth elements – ppm…
 Cut off Grade : The minimum concentration or grade of mineral that is
required for rock to be considered ore.
 Waste : Not Ore.
 Ore Body: A mineralized deposit (resource) whose characteristics have
been examined and found to be commercially viable. The extents of the ore
body are determined by the cut-off grade.
 Host Rock: The rock containing an ore deposit. Typically composed of 2
or more minerals.
 Gangue: Minerals in the ore body that are not of economic interest
 Mineral Processing

Is the recovery of valuable minerals from ore

Takes place in a mill, aka concentrator - because it
concentrates valuable minerals by removing unwanted
material.
The two main products are the concentrate streams
(valuable minerals) and the tailings streams (rejects).
Disciplines related to mineral processing
Fields of Metallurgical Engineering
Description Example of topics
Field
Theory and practice of
liberation of minerals
Crushing and grinding,
Beneficiation or from ores and their
magnetic and electrical
Mineral Dressing separation by physical
methods, flotation, etc.
methods at ambient
conditions
Mineral Processing
Chemical methods
sometimes at high
Leaching, precipitation,
temperature and pressure
Extractive metallurgy electrolysis, oxidation,
for treating ores to
reduction, etc.
recover their metal
values in a pure form

Study of physical Crystal structure, effect

properties of metals and of impurities,
Physical metallurgy
alloys, preparation of metallography, heat
alloys treatment, etc.
Processing of metals in
Engineering metallurgy Casting, welding, etc.
Metal Processing the molten state
Processing of metals in Forging, rolling,
Mechanical metallurgy
the solid state extrusion, piercing
Processing of metal Preparation of metals in
Powder metallurgy powders into finished powder form, hot
products pressing, etc.
 Engineering Terminology in Mineral
Processing

 Circuit: The path that the ore that is being

processed takes as it proceeds from one
processing point to another.
 Flow Sheet - Drawing that indicates the path
that the mineral takes within a process. Several
circuits are often contained within a flow sheet
 Recovery Rate – The percentage of valuable
metal/mineral, by mass, in the concentrate
from the feed
 Mineral Processing
The goals of mineral processing are to:

separate economic mineral particles from waste or gangue

subject minerals to processes in order to concentrate them or to
extract metals from them
Many forms of mineral processing
Depends on feed material and desired product
 Mineral Processing Terminology

 Concentration: Another word for grade

 Heads: A term that is used to denote the mineral
found in the FEED to a circuit.
 Head Grade: aka feed concentration
 Concentrate: a purified mineral. May require further
downstream processing to convert for end uses.
Examples: Copper and nickel sulfides
 Tailings - Material rejected from a mill after the
recoverable valuable minerals have been extracted.
 Industrial mineral: is used for end purpose without
chemical alteration. Examples: gravel, coal
 Mineralogy: Description of mineral contents
 What is mineral processing?
Mineral:
a)A solid naturally-occurring compound having a definite chemical
composition.

b) Inorganic substance that are extracted from the earth for use by man.

c) A naturally occurring inorganic element or compound having an

orderly internal structure and characteristic chemical composition,
crystal form, and physical properties.
 Mineral classification
Nonmetallic processing has some commonalities
with metal processing, but lots of differences
Examples of minerals
Examples of minerals
Mineralogy determines recoverability
Impact of mineralogy

We mine rocks but we

concentrate
minerals.
Gangue minerals also
important
Understanding
mineralogy allows
design of
processes
Important for
feasibility studies
 What is mineral processing?
Processing –
Extract values, reject waste
Conversion of mined ore into usable product

More expensive/challenging with lower grade ores

Numerous processing methods
 Mineral Processing Methods =
beneficiation + extractive metallurgy

Beneficiation aka Mineral Dressing

Overlap of physical and chemical methods, depending on product
Where extractive metallurgy leaves off, metal processing begins
 Mineral Processing Terminology

 Beneficiation: enrichment of ores and separation of unwanted

gangue minerals
◦ subsequent metals extraction more efficient.
◦ Can be divided into two distinct steps:
◦ Liberation: the rock is broken down by mechanical means,
mineral components become independent of each other,
detached Separation: valuable minerals are separated by
means of physical and physico-chemical methods making use
of differences in specific gravity, magnetic properties, etc.

 Extractive metallurgy:
◦ Chemical reactions of the processes
◦ equipment where reactions take place
◦ Flowsheets – combinations of processes
Typical Beneficiation Steps
 Beneficiation Terminology
 Comminution: Reduction of particle size

◦ Starts at mine with blasting

 Two basic types of equipment used:

◦ Crushing – breakage by compression

◦ Grinding – breakage by abrasion and impact

Comminution Equipment

Shaft
Comminution Equipment

Shaft
 Beneficiation Terminology

 Classification : Separation based mainly on particle size

 Behavior affected by size, shape, and density of the

particles

 Two common types of classifiers:

◦ Screens – dry method, coarser particles

◦ Hydrocyclones – wet method, finer particles

Classification Equipment
 Beneficiation Terminology

 Separation Techniques take advantage of the

differences in characteristics between minerals:
◦ Flotation: Attachment of minerals to air bubbles -
hydrophibicity
◦ Magnetic Separation: Apply magnetic field
◦ Gravity Separation: differences in specific gravity of
materials
◦ Electrostatic Separation: Apply electrostatic polarity
 Particle size distribution has large influence on
results
 Separation Equipment
 Flotation cell
Separation Equipment
 Magnetic
separator
 Separation Equipment
 Gravity separation - jig
 Separation Equipment
 Electrostatic
separator
 Beneficiation Terminology
 Dewatering: To remove water from a substance.
Also refers to the circuit where this takes place.

 Dewatering Techniques:
◦ Thickener: Allow gravity settling
◦ Filter: Apply air pressure to draw water out
◦ Centrifuge: Apply centrifugal force
◦ Dryer: Apply heat to evaporate

 Slurry Density: The amount of solids in a slurry,

expressed as a percentage by weight.
Dewatering Equipment
 Thickener
 Dewatering Equipment
 Disc filter
 Dewatering Equipment
 Rotary kiln dryer
 Beneficiation Terminology
 Waste Disposal - "Mining is waste management ..."
◦ The majority of tonnage mined must be disposed of as tailings
◦ Water used must be treated and released

 Tailings Dam: Built from ground waste rock discharged after

processing from the mill

 Acid Mine Drainage: produced by exposing sulfide minerals to air and

water, resulting in oxidation that generates acid.

 Waste Rock: Unprocessed non-mineralized / low grade mined material

 Water Balance: Accounting of water inputs and outputs from a mine/mill

site.

 Water Treatment: The removal of harmful contaminants from water

Waste Disposal
 Tailings Dam
Waste Disposal
Waste Rock Pile
 Waste Disposal
 Acid Mine Drainage
 Waste Disposal
 Water Balance
 Mineral Processing Methods =
beneficiation + extractive metallurgy

Beneficiation aka Mineral Dressing

Overlap of physical and chemical methods, depending on product
Where extractive metallurgy leaves off, metal processing begins
Extractive Metallurgy Terminology
 Hydrometallurgy
◦ Leaching - the process of extracting a soluble
constituent from a solid by means of a (water based)
solvent
 Water changes solubility, by making it acidic or
basic, oxidizing or reducing
◦ Solvent Extraction – transfer between immiscible
fluids
◦ Ion Exchange – solid resins that adsorb dissolved
chemical species
◦ Precipitation – convert dissolved into solid
 Crystallization via evaporation
 Ionic precipitation - addition of a reagent to a
solution creates a metal compound whose solubility
is so low that precipitation takes place immediately
Hydrometallurgy Equipment
 Tank leach circuit
Hydrometallurgy Equipment
 Solvent extraction mixer-settlers
Hydrometallurgy Equipment
 Ion Exchange
Hydrometallurgy Equipment
 Vacuum
crystallizer
Extractive Metallurgy Terminology
 Pyrometallurgy – use of heat to induce a
chemical transformation

◦ Roasting – convert to oxide form. Example: 2

CuS2 + 5 O2 → 2 CuO + 4 SO2

◦ Smelting - uses reducing substances that will

combine with those oxidized elements to free the
metal. Example:
2 Fe2O3 + 3 C → 4 Fe + 3 CO2
Pyrometallurgy Equipment
 Smelter
Extractive Metallurgy Terminology
 Electrometallurgy – use of electrical energy to
induce a chemical transformation

◦ Electrowinning – to precipitate a metal from

solution using electric potential
◦ Electrorefining – to purify a metal by dissolving it,
then re-precipitating it
Electrometallurgy Equipment
 Alternating anodes and cathodes in a
tankhouse for electrowinning
 Flowsheet examples
 Aluminum: from bauxite
 Copper: from chalcopyrite
 Iron: from hematite
 Gold – Placer, sulphide and oxide
 Oil Sands – Fort McMurray
Aluminum
Copper
Iron
Gold
Oil Sands
Mineral Processing Recovery
 Recovery : Potential for loss every step of the way, in each
circuit!
 Tonnage vs. Recovery: A processing circuit pushed beyond
its capacity will induce recovery loss
 Feed Grade vs. Recovery : A higher feed grade tends to
have higher processing recovery
 Concentrate Grade vs. Recovery: A higher concentrate
grade tends to result in lower processing recovery (=
rejection of lower quality minerals to tailings)
 Concentrate Grade vs. Price: A higher quality concentrate
will fetch a higher price (have lower impurity penalties)

 Revenue = Production (tonnes) x grade x recovery x price

 Mining Economics
 Typical product grade vs. recovery curve
for a Cu sulphide flotation mill
Mining Economics
 Relation between cost and particle size
 Mineral Economics - Review
 Discounted Cash Flow (DCF)
◦ NPV (net present value) is a means of comparing a
dollar today to the value of the same dollar in the
future. For mining projects, we apply NPV to
determine if a project is worth more than it costs.
◦ Free Cash Flow (FCF) is the operating cash flow minus
capital includes Taxes, Dividends, Royalties,
Depreciation and Amortization. I.e. the amount of
money left after the bills are paid
◦ Discount Rate is rate that future cash flows are
discounted to determine present value. This is
different than interest.
◦ IRR (internal rate of return) is the discount rate that
results in an NPV of 0.
Mineral Economics - Review
Net Present Value is common way to evaluate a
project
Value = Free Cash Flow
Rate = Discount Rate
n=Total number of periods
i=Period

Payback period - the time required for the operating revenue to pay
back all the costs, including the initial capital investment used to
construct the project.
 Mineral Economics
 Typical mining project annual cash flow pattern
 R = revenue, C = costs, T = taxes, A = annual
loan payment (principal + interest), F = cash
flow and K= capital costs.
Mining Project Economics

 What happens when project parameters are changed?

 Must start with a reasonable base case scenario (technically
feasible) before economic optimization (fine tuning)
 Strong inter-relationships between:
◦ Tonnage
◦ Grade
◦ Capital costs
◦ Operating costs

 Has effects on:

◦ Mine life
◦ Cutoff grade
Capital and Operating Cost Estimation vs. Tonnage

 Work by OHara (1980), OHara and Suboleski (1992) and USBM

(1987) suggest that the curves for capital and operating costs
can be reasonably approximated by exponential equations,
with the general form:
 Cost = K tx
Where:
K = a constant specific to the particular cost
t = production rate in tonnes per day
x = an exponent
 Capital costs typical range: 0.5 to 0.7
◦ 0.6 is a reasonable first estimate
 Operating costs in $/t typical range -.3 to -.1
◦ -0.2 is a reasonable first estimate
 WARNING: These equations should not be used for detailed
estimating, although they can give guidance for order of
magnitude estimating.
Capital and Operating Costs vs. Tonnage

 If a cost is known accurately, this relationship can be used to factor the cost up or
down for differing production rates, within reasonable limits:
 Cost at t1 = C1 = K t1x
Cost at t2 = C2 = K t2x
Then:
C1 / C2 = (K t1x) / (K t2x)
= t1x / t2x (because K is common it can be eliminated)
= (t1 / t2)x
Simplified: C1 / C2 = (t1 / t2)x
Then: C2 = C1 (t2 / t1)x
 For a capital cost or annual operating cost, if C1 and t1 are known, and x can be
estimated from experience then C2 can be estimated for a given t2.
 Example:
 For capital cost at 20,000 t/d is $30 million, then at 25,000 t/d can be estimated
at:
 C2 = $30000000 (25000 / 20000)0.6
= $30000000 (1.1433)
= $34,298,000
 For operating cost of $10.00/tonne, and an exponent of -.2 the unit cost at the
higher tonnage will be:
C2 = $10.00 (25000 / 20000)-0.2
= $10.00 (0.9564) = $9.56
Capex and Opex vs. Production Rate
 NPV Curve

 An NPV curve is theoretical, always check

that the inputs are realistic!
Mineral Economics – Operating Costs

 Overall operating costs are broken down into 3 basic

areas for economic analysis:
◦ Mining – determine mine plan input costs, production
rate and fully diluted (Run-of-Mine = ROM) grade
◦ Milling – determine process flowsheet input costs,
recovery rate, product quality
◦ General and Administrative (G & A) – determine
overhead costs :
 Administration (HR, payroll)
 Management (site + head office)
 Safety & Health
 Environment
 Quality Management
G&A tends to be fixed REGARDLESS of production rate!
 Milling Operating Costs

Typical relative cost of beneficiating an ore

%
Operation
Crushing 5 - 20
Grinding 25 - 75
Flotation 25 -45
Dewatering and
10 -20
drying
Other operations 5 - 10
Project Stages

 Idea stage
 Conceptual stage
 Pre-feasibility stage
 Market Studies
 Feasibility studies
 Financial analysis
 Preliminary design
 Final design and construction
 Commissioning and start up
 Closing reports
Typical Project Stages

 Idea Stage : identify the need for a project to be started or

conceptualized
◦ philosophic - decide whether this is the type of project that
they would like to pursue
◦ Discussions of cost and schedule at the idea stage are normally
limited to a broad definition
◦ Informal - sometimes mentioned to get a reaction
◦ Ideas can begin with anyone in the organization

 Conceptual Study: establish the shape of the project, and get a

better feel for its scope and size
◦ Costs can be put to a concept. However, the accuracy of
investment costs may be wildly out, probably +/-50%.
◦ Rough estimate based on experience and judgment
◦ Estimate's usefulness is in establishing an idea of the costs
commensurate with the aims of the project
Resource and Reserve Categorization
 Mineral Reserve: This is where things start to get real
Typical Project Stages

 Pre-feasibility Study : comprehensive study of viability of a

mineral project
◦ mining method has been established
◦ effective method of mineral processing has been determined
◦ financial analysis based on reasonable assumptions of
technical, engineering, legal, operating, economic, social, and
environmental factors
◦ determine if all or part of the mineral resource may be
classified as a mineral reserve

 Feasibility Study: comprehensive study of a mineral deposit

◦ all geological, engineering, legal, operating, economic, social,
environmental and other relevant factors are considered in
sufficient detail
◦ could reasonably serve as the basis for a final decision by a
financial institution to finance the development of the deposit
for mineral production.
Typical Project Stages

 Detailed design and construction: Engineering design and

construction are inseparable, even though two distinct groups
normally perform the work.
◦ Preliminary design - establish a definite time frame for freezing
the process and plant designs so that cost and schedule upsets
are minimized effective method of mineral processing has been
determined
◦ definitive estimate to an accuracy of 10 to 15% to control the
job – requires about 20 percent of the total engineering must
be done, as measured by completion of drawings.
◦ be leery of both steam-rolling a design freeze prematurely, vs.
allowing people to continuously change their minds

 Commissioning: checkout period prior to starting the plant

◦ Sometimes the entire plant is run for a period of time without
material
◦ Startup usually begins on a reduced output basis, gradually
increasing until planned output capacity is reached
Typical Project Stages

 Project emotional stages:

◦ Euphoria
◦ Wandering off track
◦ Catch up and control
◦ The Boggs
◦ Project Manager panic
◦ Frantic catch up and control
◦ Loose ends
◦ Sign off
LIBERATION, SEPARATION,
EXTRACTION

STAGE 1 - Blasting
STAGE 2 - Primary Crushing
STAGE 3 - Secondary Crushing
STAGE 4 - Grinding
STAGE 5 - Separation by size
STAGE 6 - Separation by values
STAGE 7 - Extraction of values
 Crushing is the first mechanical stage in the
process of comminution in which the main
objective is the liberation of the valuable
minerals from the gangue.

 The ore must be crushed to appreciable size

before effective mineral extraction can be
embarked on
 The relation between the size of the feed and
the size of the discharge material in crushers
is known as the reduction ration

 NB: All crushers have a limited reduction

ratio.
 When designing a crushing circuit it is standard
to distribute the crushing work over a number of
crushers for the following reasons:

 This is to accommodate the crusher’s reduction

ratio

 To improve the throughput of the crushers

 Minimize the chances of blockages and

overloading
 The number of crushing stages is guided by
the feed and expected outlet particulate size.

 Stage 1 – Jaw Crusher

 Stage 2 – Cone Crusher
 Stage 3 – Cone Crusher
 Crushing and Screening

 Crushing – primary, secondary and tertiary

 Primary crusher – carried out in a heavy duty

machine capable of high tonnages Jaw Crusher

 Vibrating Feeder – to provide a constant

regulated flow of ore to the conveyor that feeds
the secondary crusher at a prescribed rate
 Over belt Magnet – designed to remove tramp
metal from the crusher feed.

 The unit simply suspends above the conveyor

belt and lifts tramp metal from the product
burden as it passes through the powerful
magnetic field
 Secondary and Tertiary Crushers

 NB – these crushers are lighter duty and are

designed to accept smaller feed size.

 Cone crushers - The crusher has a cone

crushing head supported within a cone
shaped bowl. The cone forms the crushing
head and rotates within the cone and the
bowl on an eccentric shaft.
 Tertiary Crusher – achieves the final
preparation of the crushed rock for milling
 Screening

What is the main purpose?

 The screen has many openings with uniform
dimensions
 Material forms a bed while it is moving across

the screen

 The bed is kept ‘alive’ by the vibrating action

so as to allow particles which may be lying on
top of the bed to move done to the screen
deck where they have the opportunity to go
through the apertures.
 Banana Screen Concept
Vibrating Screen
 MILLING SECTION
 Mineral of interest is usually locked in the
gangue and must first be unlocked or
liberated before separation can be done.

 The main objective of the milling process is

liberation.
Conical Ball-Mill
 Grinding is the last stage in the process of
comminution; in this stage the particles are
reduced
in size by a combination of impact and abrasion,
either dry or in suspension in water.

 It is performed in rotating cylindrical steel vessels

which contain a charge of loose crushing bodies -
the grinding medium- which is free to move
inside the mill, thus comminuting the ore
particles.
 The grindability of a rock is the ease with
which material can be comminuted.

 The most widely used parameter for

measuring grindability is the Bond Work
Index

 Bond Work Index – represents the materials

resistance to milling
 As opposed to crushing which takes place
between two rigid surfaces by compressive
forces, milling is a random process.

 It depends on the probability of an ore particle

entering the region the region between the
loose crushing bodies (grinding media)

 This causes a very wide size distribution in the

discharged particles.
 Ore is broken in mills using basically three
mechanisms:

 1. Impact

 2.Chipping

 3.Abrasion
 Grinding circuits feed can be wet or dry,
depending on the subsequent process and
the nature of the product.

 Dry grinding is necessary with some materials

due
to physical or chemical changes which occur
if water is added.
 Wet grinding is generally used in mineral
processing operations because of the overall
economies of operation.

 The advantages of wet grinding are:

 It consumes lower power per tonne of

product.
 It has higher capacity per unit mill volume.

 It makes possible the use of wet screening or

classification for close product control.
 It eliminates the dust problem.

 It makes possible the use of simple handling

and transport methods such as pumps, pipes.
 Circuits are divided into two broad
classifications: open and closed. In open
circuit the material is fed into the mill at a
rate calculated to produce the correct product
in one pass

 As a result, many particles in the product are

overground, which consumes energy
needlessly, and the product may
subsequently be difficult to treat.
 Closed-circuit grinding reduces the residence
time of particles in each pass, and so the
proportion
of finished sizes in the mill, compared with
open circuit
grinding.
• This decreases overgrinding and increases the
energy available for useful grinding as long as
there is an ample supply of unfinished material
present.

 As the tonnage of new feed increases, so the

tonnage of circulating load increases, since the
classifier underflow becomes coarser, but the
composite mill feed becomes finer due to this
increase in circulating load.
 ). This type of circuit is rarely used
 in mineral processing applications as there is

no
 control on product size distribution. The feed

rate
 must be low enough to ensure that every

particle
 spends enough time in the mill to be broken

down
 to product size.
 Mill Feed Control

Feed to the mill must be controlled in order to

ensure that a constant ffed rate to the mills is
maintained.
This is very important because overfeeding or
underfeeding has the following effects :
 Over feeding
 1. Poor grinds due to reduced mill efficiency
 2.Hihg mill reject losses
 3.Increase in recirculating load

 Underfeeding
 1.Low densities
 2.Increased rate wear of mill liners
 3.Over grinding leading to excessive liberation
of talc which make flotation difficult
 Primary Mills & Cyclones

 Primary ball mills grind material into slurry which is

subsequently pumped into to cyclones.

 Overflow is passed over a linear screen for trash

removal and then into flash cells.

 Underflow gravitates back to PBM feed hopper

 The process of returning cyclone underflow to the mill

constitutes the closed milling circuit.

 This essentially means that all material which is still

coarse is returned to the mill for further grinding
Grinding Mills
Tube Mill
 Control of the grinding circuit

 The purpose of milling is to reduce the size

of the ore particles to the point where
economic liberation of the valuable minerals
takes place.
 The principal variables which can affect control are:

 changes in the new feed rate and the circulating

load

 size distribution

 hardness of the ore

 rate of water addition to the circuit.

 Also important are interruptions in the
operation of the circuit, such as stoppages
for such reasons as to feed new grinding
medium or to clear a choked cyclone.
 Fluctuation in feed size and hardness are
probably the most significant factors
disturbing the balance of a grinding circuit.

 Such fluctuations may arise from differences

in composition, mineralisation, grain size,
and crystallisation of the ore from different
parts of the mine, from changes in the
crusher settings, often due to wear, and from
damage to screens in the crushing circuit.
 Minor fluctuations can be smoothed out by blending
material excavated at different points in space and time.

 In implementing instrumentation and process control for

grinding circuits the control objective must first be
defined, which may be:
 (1) to maintain a constant product size at maximum

throughput
(2) to maintain a constant feed rate within a limited range of
product size
(3)to maximise production per unit time in conjunction with
downstream circuit performance(e.g. flotation recovery).
 It is therefore ore feed rate and water
addition to the mill and classifier which are
the major variables used to control grinding
circuits.
 CLASSIFICATION
 Classification is a method of separating
mixtures of minerals into two or more
products on the basis of the velocity with
which the grains fall through a fluid medium
 In mineral processing, this is usually water,
and wet classification is generally applied to
mineral particles which are considered too
fine to be sorted efficiently by screening.
 Since the velocity of particles in a fluid
medium is dependent not only on the size,
but also on the specific gravity and shape of
the particles, the principles of classification
are important in mineral separations utilising
gravity concentrators.
 Principles of classification

 When a solid particle falls freely in a vacuum,

it is subject to constant acceleration and its
velocity increases indefinitely, being
independent of size and density.

 Thus a lump of lead and a feather fall at

exactly the same rate.
 In a viscous medium, such as air or water,
there is resistance to this movement and the
value increases with velocity.

 When equilibrium is attained between the

gravitational and fluid resistances forces, the
body reaches its terminal velocity and
thereafter falls at a uniform rate.
 The nature of the resistance depends on the
velocity of the descent.

 At low velocities motion is smooth because the

layer of fluid in contact with the body moves with
it, while the fluid a short distance away is
motionless.

 Between these two positions is a zone of intense

shear in the fluid all around the descending
particle.
 Effectively all resistance to motion is due to
the shear forces or viscosity of the fluid and
is hence called viscous resistance.

 At high velocities the main resistance is due

to the displacement of fluid by the body, and
viscous resistance is relatively small; this is
known as turbulent resistance.
 Whether viscous or turbulent resistance
predominates, the acceleration of particles in a fluid
rapidly decreases and the terminal velocity is quickly
reached.

 Classifiers consist essentially of a sorting column in

which a fluid is rising at a uniform rate

 Particles introduced into the sorting column either

sink or rise according to whether their terminal
velocities are greater or lesser than the upward
velocity of the fluid.
 The sorting column therefore separates the
feed into two products - an overflow
consisting of particles with terminal velocities
lesser than the velocity of the fluid and an
underflow or spigot product of particles with
terminal velocities greater than the rising
velocity.
 diagram
 Free settling and hindered settling – refer to Newton &
Stokes’s law

 Both laws show that the terminal velocity of a particle

in a particular fluid is a function only of the particle
size and density. It can be seen that:
 (1) If two particles have the same density, then the
particle with the larger diameter has the higher
terminal velocity.

 (2) If two particles have the same diameter, then the

heavier particle has the higher terminal velocity
 Density differences between the particles has a
more pronounced effect on classification
coarser size ranges.

 This is important where gravity concentration is

being utilised. Over-grinding of the ore must be
avoided, such that particles are fed to the
separator in as coarse a state as possible, so
that a rapid separation can be made, exploiting
the enhanced effect of specific gravity
difference.
 Types of classifiers

 Many different types of classifier have been

designed and built.

 They may be grouped, however, into two

broad classes depending on the direction of
flow of the carrying current.
 Horizontal current classifiers such as
mechanical classifiers are essentially of the
free-settling type and accentuate the sizing
function.

 Vertical current or hydraulic classifiers are

usually hindered-settling types and so
increase the effect of density on the
separation.
 Hydraulic classifiers

 These are characterised by the use of water

additional to that of the feed pulp, introduced so
that its direction of flow opposes that of the
settling particles.

 They normally consist of a series of sorting

columns through each of which a vertical current
of water is rising and particles are settling out.
 Mechanical classifiers

 Several forms of classifier exist in which the

material of lower settling velocity is carried
away in a liquid overflow, and the material of
higher settling velocity is deposited on the
bottom of the equipment and is dragged
upwards against the flow of liquid by some
mechanical means.
 One of the major disadvantages of the
mechanical classifier is its inability to produce
overflows of very fine particle size at
reasonable pulp densities.
 THE HYDROCYCLONE

 This is a continuously operating classifying

device that utilises centrifugal force to accelerate
the settling rate of particles.

 It is one of the most important devices in the

minerals industry, its main use in mineral
processing being as a classifier, which has
proved extremely efficient at fine separation
sizes.
 It has replaced mechanical classifiers in many
applications, its advantages being simplicity
and high capacity relative to its size.

 The feed is introduced under pressure

through the tangential entry which imparts a
swirling motion to the pulp.

 This generates a vortex in the cyclone, with a

low-pressure zone along the vertical axis.
 An air core develops along the axis, normally
connected to the atmosphere through the apex
opening, but in part created by dissolved air
coming out of solution in the zone of low
pressure.

 The classical theory of hydrocyclone action is

that particles within the flow pattern are
subjected to two opposing forces- an outward
centrifugal force and an inwardly acting drag
 The centrifugal force developed accelerates
the settling rate of the particles thereby
separating particles according to size, shape,
and specific gravity.

 Faster settling particles move to the wall of

the cyclone, where the velocity is lowest, and
migrate to the apex opening.

 Diagram
 Due to the action of the drag force, the
slower-settling particles move towards the
zone of low pressure along the axis and are
carried upward through the vortex-finder to
the overflow.

 The existence of an outer region of

downward flow and an inner region of
upward flow implies a position at which there
is no vertical velocity.
 This applies throughout the greater part of
the cyclone body, and an envelope of zero
vertical velocity should exist throughout the
body of the cyclone

 Particles thrown outside the envelope of zero

vertical velocity by the greater centrifugal
force exit via the underflow, while particles
swept to the centre by the greater drag force
leave in the overflow.
 Particles lying on the envelope of zero velocity
are acted upon by equal centrifugal and drag
forces and have an equal chance of reporting
either to the underflow or overflow.

 Hydrocyclones are almost universally used in

grinding circuits because of their high capacity
and relative efficiency. They can also classify
over a very wide range of sizes (typically 5-
500micrometers), smaller diameter units being
used for finer classification.
 Factors affecting cyclone performance

 The empirical models and scale-up

correlations, tempered by experience, are
helpful in summarising the effects of
operating and design variables on cyclone
performance.
 The following process trends generally hold
true:

 Classification efficiency
 Increases with correct cyclone size selection
 Decreases with feed solids concentration

and/or viscosity
 Increased by limiting water to underflow
 Increased by certain geometries
 Flow split of water to under flow

 Increases with larger apex or smaller vortex

 finder
 Decreases with flow-rate
 Decreases with inclined cyclones (especially

low pressure)
 Increases with feed solids concentration

and/or
viscosity
 Flow rate

 Increases with pressure

 Increases with cyclone diameter
 Decreases (at a given pressure) with feed

solids
 concentration and/or viscosity
 Cut-size (inversely related to solids recovery)
 Increases with cyclone diameter
 Increases with feed solids concentration

and/or
 viscosity
 Decreases with flow rate
 Increases with small apex or large vortex

finder
 Increases with cyclone inclination to vertical
 Since the operating variables have an
important effect on the cyclone performance,
it is necessary to avoid fluctuations in flow
rate, etc., during operation.

 Pump surging should be eliminated either by

automatic control of level in the sump, or by
a self-regulating sump, and adequate surge
capacity should be installed to eliminate flow
rate fluctuations.
 Read on Gravity Separation
 FROTH FLOTATION
 Flotation is undoubtedly the most important
and versatile mineral processing technique,
and both its use and application are
continually being expanded to treat greater
tonnages and to cover new areas.

 Originally patented in 1906, flotation has

permitted the mining of low-grade and
complex ore bodies which would have
otherwise been regarded as uneconomic.
 Flotation is a selective process and can be used
to achieve specific separations from complex
ores such as lead-zinc, copper-zinc, etc.

 Initially developed to treat the sulphides of

copper, lead, and zinc, the field of flotation has
now expanded to include platinum, nickel, and
gold-hosting sulphides, and oxides, such as
hematite and cassiterite, oxidised minerals, such
as malachite and cerussite, and nonmetallic
ores, such as fluorite, phosphates, and fine coal.
 Principles of flotation

 Flotation is a physico-chemical separation

process that utilises the difference in surface
properties of the valuable minerals and the
unwanted gangue minerals.

 The theory of froth flotation is complex,

involving three phases (solids, water, and froth)
with many sub-processes and interactions
 The process of material being recovered by
flotation from the pulp comprises three
mechanisms:

 Selective attachment to air bubbles (or "true

flotation").
 Entrainment in the water which passes through

the froth.
 Physical entrapment between particles in the

froth attached to air bubbles (often referred to as

"aggregation").
 The attachment of valuable minerals to air
bubbles is the most important mechanism and
represents the majority of particles that are
recovered to the concentrate.

 Although true flotation is the dominant

mechanism for the recovery of valuable mineral,
the separation efficiency between the valuable
mineral and gangue is also dependent on the
degree of entrainment and physical entrapment.
 Unlike true flotation, which is chemically
selective to the mineral surface properties,
both gangue and valuable minerals alike can
be recovered by entrainment and entrapment.

 Drainage of these minerals occurs in the froth

phase and controlling the stability of this
phase is important to achieve an adequate
separation.
 In industrial flotation plant practice,
entrainment of unwanted gangue can be
common and hence a single flotation stage is
uncommon.

 Often several stages of flotation (called

"circuits") are required to reach an
economically acceptable quality of valuable
mineral in the final product.
 True flotation utilises the differences in
physicochemical surface properties of
particles of various minerals.

 After treatment with reagents, such

differences in surface properties between the
minerals within the flotation pulp become
apparent and, for flotation to take place, an
air bubble must be able to attach itself to a
particle, and lift it to the water surface.
 The diagram below illustrates the principles
of flotation in a mechanical flotation cell.

 The agitator provides enough turbulence in

the pulp phase to promote collision of
particles and bubbles which results in the
attachment of valuable particles to bubbles
and their transport into the froth phase for
recovery
 The process can only be applied to relatively fine
particles, because if they are too large the adhesion
between the particle and the bubble will be less than
the particle weight and the bubble will therefore drop
its load.

 There is an optimum size range for successful

flotation

 In flotation concentration, the mineral is usually

transferred to the froth, or float fraction, leaving the
gangue in the pulp or tailing.
 This is direct flotation and the opposite is
reverse flotation, in which the gangue is
separated into the float fraction.

 The function of the froth phase is to enhance

the overall selectivity of the flotation process.
The froth achieves this by reducing the
recovery of entrained material to the
concentrate stream, while preferentially
retaining the attached material.
 This increases the concentrate grade whilst
limiting as far as possible the reduction in
recovery of valuables

 The relationship between recovery and grade

is a trade-off that needs to be managed
according to operational constraints and is
incorporated in the management of an
optimum froth stability.
 As the final separation phase in a flotation
cell, the froth phase is a crucial determinant
of the grade and recovery of the flotation
process.

 The mineral particles can only attach to the

air bubbles if they are to some extent water-
repellent, or hydrophobic.
 Having reached the surface, the air bubbles
can only continue to support the mineral
particles if they can form a stable froth,
otherwise they will burst and drop the
mineral particles.
 To achieve these conditions it is necessary to
use the numerous chemical compounds
known as FLOTATION REAGENTS.

 The activity of a mineral surface in relation to

flotation reagents in water depends on the
forces which operate on that surface.
 The hydrophobicity of a mineral therefore
increases with the contact angle; minerals
with a high contact angle are said to be
aerophilic, i.e. they have a higher affinity for
air than for water.
 The terms hydrophobicity and floatability are
often used interchangeably.

 Hydrophobicity, however, refers to a

thermodynamic characteristic, whereas
floatability is a kinetic characteristic and
incorporates other particle properties
affecting amenability to flotation
 Most minerals are not water-repellent in their
natural state and flotation reagents must be
added to the pulp.

 The most important reagents are the

collectors, which adsorb on mineral surfaces,
rendering them hydrophobic (or aerophilic)
and facilitating bubble attachment
 The frothers help maintain a reasonably
stable froth.

 Regulators are used to control the flotation

process; these either activate or depress
mineral attachment to air bubbles and are
also used to control the pH of the system.
 Classification of minerals

 All minerals are classified into polar or non-

polar types according to their surface
characteristics. The surfaces of non-polar
minerals are characterised by relatively weak
molecular bonds.
 The minerals are composed of covalent
molecules held together by van der Waals
forces, and the non-polar surfaces do not
readily attach to the water dipoles, and in
consequence are hydrophobic.

 Minerals of this type, such as graphite,

sulphur, molybdenite, diamond, coal and talc,
thus have high natural floatabilities with
contact angles between 60 and 90 ~
 Although it is possible to float these minerals
without the aid of chemical agents, it is universal
to increase their hydrophobicity by the addition
of hydrocarbon oils or frothing agents.

 Minerals with strong covalent or ionic surface

bonding are known as polar types, and exhibit
high free energy values at the polar surface. The
polar surfaces react strongly with water
molecules, and these minerals are naturally
hydrophilic.
 In general, therefore, the degree of polarity
increases from sulphide minerals, through
sulphates, to carbonates, halites, phosphates,
etc., then oxides-hydroxides, and, finally,
silicates and quartz.
 Collectors

 Hydrophobicity has to be imparted to most

minerals
in order to float them.

 In order to achieve this, surfactants known as

collectors are added to the pulp and time is
allowed for adsorption during agitation in
what is known as the conditioning period.
 Collectors are organic compounds which
render selected minerals water-repellent by
adsorption of molecules or ions on to the
mineral surface, reducing the stability of the
hydrated layer separating the mineral surface
from the air bubble to such a level that
attachment of the particle to the bubble can
be made on contact.
 Collector molecules may be ionising
compounds, which dissociate into ions in
water, or non-ionising compounds, which are
practically insoluble, and render the mineral
water-repellent by coveting its surface with a
thin film.

 Ionising collectors have found very wide

application in flotation .
 They have complex molecules which are
asymmetric in structure and are heteropolar,
i.e. the molecule contains a non-polar
hydrocarbon group and a polar group which
may be one of a number of types. The non-
polar hydrocarbon radical has pronounced
water-repellent properties, whereas the polar
group reacts with water.
 Ionising collectors are classed in accordance
with the type of ion, anion or cation that
produces the water-repellent effect in water.

 The structure of sodium oleate, an anionic

collector in which the hydrocarbon radical,
which does not react with water, constitutes
the non-polar part of the molecule,
 Amphoteric collectors possess a cationic and an
anionic function, depending on the working pH,
and have been used to treat sedimentary
phosphate deposits.

 Because of chemical, electrical, or physical

attraction between the polar portions and
surface sites, collectors adsorb on the particles
with their non-polar ends orientated towards
the bulk solution, thereby imparting
hydrophobicity to the particles.
 They are usually used in small amounts,
substantially those necessary to form a
monomolecular layer on particle surfaces
(starvation level), as increased concentration,
apart from the cost, tends to float other
minerals, reducing selectivity.

 It is always harder to eliminate a collector

already adsorbed than to prevent its
adsorption.
 An excessive concentration of a collector can
also have an adverse effect on the recovery of
the valuable minerals, possibly due to the
development of collector multi-layers on the
particles, reducing the proportion of
hydrocarbon radicals orientated into the bulk
solution.
 The hydrophobicity of the particles is thus
reduced, and hence their floatability.

 The flotation limit may be extended without

loss of selectivity by using a collector with a
longer hydrocarbon chain, thus producing
greater water repulsion, rather than by
increasing the concentration of a shorter
chain collector.
 However, chain length is usually limited to
two to five carbon atoms, since the solubility
of the collector in water rapidly diminishes
with increasing chain length and, although
there is a corresponding decrease in
solubility of the collector products, which
therefore adsorb very readily on the mineral
surfaces, it is, of course, necessary for the
collector to ionise in water for chemisorption
to take place on the mineral surfaces.
 Not only the chain length but also the chain
structure, affects solubility and adsorption
branched chains have higher solubility than
straight chains.

 It is common to add more than one collector

to a flotation system.
 A selective collector may be used at the head
of the circuit, to float the highly hydrophobic
minerals, after which a more powerful, but
less selective one, is added to promote
recovery of the slower floating minerals.

 Read on anionic and cationic collectors.

 Frothers

 Frothers are added to stabilise bubble

formation in the pulp phase, to create a
reasonably stable froth to allow selective
drainage from the froth of entrained gangue,
and to increase flotation kinetics.
 Frothers are in many respects chemically similar
to ionic collectors, and, indeed, many of the
collectors, such as oleates, are powerful
frothers, being in fact too powerful to be used as
efficient frothers, since the froths which they
produce can be too stable to allow efficient
transport to further processing.

 Froth build-up on the surfaces of thickeners and

excessive frothing of flotation cells are problems
occurring in many mineral processing plants.
 A good frother should have negligible
collecting power, and also produce a froth
which is just stable enough to facilitate
transfer of floated mineral from the cell
surface to the collecting launder.

 Frothers are generally heteropolar surface-

active organic reagents, capable of being
adsorbed on the air-water interface.
 When surface-active molecules react with
water, the water dipoles combine readily with
the polar groups and hydrate them, but there
is practically no reaction with the non-polar
hydrocarbon group, the tendency being to
force the latter into the air phase.
 Thus the heteropolar structure of the frother
molecule leads to its adsorption, i.e. the molecules
concentrate in the surface layer with the non-polar
groups oriented towards the air and the polar groups
towards the water.

 Diag

 Frothing action is thus due to the ability of the

frother to adsorb on the air-water interface because
of its surface activity and to reduce the surface
tension, thus stabilising the air bubble.
 Frothers must be to some extent soluble in water,
otherwise they would be distributed very unevenly in
an aqueous solution and their surface-active
properties would not be fully effective. The most
effective frothers include in their composition one of
the following groups:

 Hydroxyl
 Carboxyl
 Carbonyl
 Amino group
 Sulpho group
 The acids, amines, and alcohols are the most
soluble of the frothers.

 The alcohols (~OH) are the most widely used,

since they have practically no collector
properties, and in this respect are preferable to
other frothers, such as the carboxyls, which are
also powerful collectors; the presence of
collecting and frothing properties in the same
reagent may make selective flotation difficult.
 Frothers with an amino group and certain
sulpho group frothers also have weak collector
properties.

 Pine oil, which contains aromatic alcohols, the

most active frothing component being terpineol,
C10H17OH, has been widely used as a frother.

 Cresol (cresylic acid), CH3C6H4OH, has also

hadwide use.
 A wide range of synthetic frothers, based
mainly on high molecular-weight alcohols,
are now in use in many plants.

 They have the important advantage over

industrial products such as pine oil and
cresol in that their compositions are much
more stable, which makes it easier to control
the flotation process and improves
performance.
 A widely used synthetic alcohol frother is
methyl isobutyl carbinol (MIBC).

 Another range of synthetic frothers are based

on polyglycol ethers, and have been found to
be very effective. They are marketed under
various names, such as Cytec Oreprep 549
and Cytec Aerofroth 65.
 Frothers based on polyglycols are also used,
and it is not uncommon to blend all three
chemical groups- alcohols, polyglycol ethers,
and polyglycols - together to provide a
specific frother for a particular flotation
circuit
 The alcohol groups provide a selective, often
brittle, froth, which allows good control and
materials transfer through the launders and
pumps. The glycol ether group is stronger, with
more persistence than the alcohol groups, while
the polyglycols are the strongest surface active
frothers utilised.

 They are very effective in maximising load

support with coarse grinds and high grade
feeds, at all pH ranges.
 Although frothers are generally surface-active
reagents, it has been shown that surface-
inactive reagents, such as diacetone alcohol and
ethyl acetal, behave as frothers in solid-liquid-
air systems, although not in two-phase liquid-
air systems.

 Molecules of these reagents have two polar

groups and are readily soluble in water. They
adsorb on solid surfaces but do not appreciably
change their hydrophobicity.
 When the mineral surface, on which the surface
inactive frother is adsorbed, is approached by
an air bubble, the molecules reorientate and
produce a sufficiently stable three-phase froth.

 Being surface inactive, these reagents do not

reduce surface tension, and apart from the
slight reduction due to collectors, the forces
available for flotation are maintained at their
maximum.
 Regulators

 Regulators, or modifiers, are used extensively in

flotation to modify the action of the collector,
either by intensifying or by reducing its water-
repellent effect on the mineral surface.

 They thus make collector action more selective

towards certain minerals. Regulators can be
classed as activators, depressants, or pH
modifiers
 Activators

 These reagents alter the chemical nature of

mineral surfaces so that they become
hydrophobic due to the action of the
collector.

 Activators are generally soluble salts which

ionise in solution, the ions then reacting with
the mineral surface.
 A classical example is the activation of sphalerite by
copper in solution. Sphalerite is not floated
satisfactorily by a xanthate collector, since the
collector products formed, such as zinc xanthate,
are relatively soluble in water, and so do not provide
a hydrophobic film around the mineral.

 Floatability can be improved by the use of large

quantities of long-chain xanthates, but a more
satisfactory method is to use copper sulphate as an
activator, which is readily soluble and dissociates
into copper ions in solution.
Activation is due to the formation of molecules of
copper sulphide at the mineral surface, due to the
fact that copper is more electronegative than zinc
and therefore ionises less readily:
ZnS + Cu 2+ = CuS + Zn 2+

The copper sulphide deposited on the sphalerite

surface reacts readily with xanthate to form
insoluble
copper xanthate, which renders the sphalerite
surface hydrophobic.
 Depressants

 Depression is used to increase the selectivity

of flotation by rendering certain minerals
hydrophilic (water-avid), thus preventing
their flotation.

 They are key to the economic flotation of

certain ores such as platinum and nickel
sulphides
 There are many types of depressants and
their actions are complex and varied, and in
most cases not fully understood, making
depression more difficult to control than the
application of other types of reagent,
particularly when the froth phase is also
affected by their action ...Makombe project
 Inorganic depressants

 Cyanides are widely used in the selective

flotation of lead-copper-zinc and copper-
zinc ores as depressants for sphalerite,
pyrite, and certain copper sulphides.

 Sphalerite rejection from copper concentrates

is often of major concern, as zinc is a penalty
element in copper smelting
 Cyanides are, of course, extremely toxic and must be
handled with great care. They also have the
disadvantage of being expensive and they depress and
dissolve gold and silver, reducing the extraction of
these metals into the froth product.

 Despite these disadvantages, they are widely used due

to their high degree of selectivity in flotation. They
also have the advantage of leaving the mineral surface
relatively unaffected, so that subsequent activation is
relatively simple, although residual cyanide ions in
solution may interfere with the activator
 Polymeric depressants

 The use of polymeric depressants has the

advantage of being less hazardous than the
more widely used inorganic depressants, and
interest in their use has been growing
 In the South African platinum group mineral
(PGM) industry, polymeric depressants such
as carboxymethyl cellulose (CMC) and guar
are widely used to depress talcaeous gangue
minerals.
 The importance of pH

It is evident from the foregoing that pulp

alkalinity
plays a very important, though very complex,
role in flotation, and, in practice, selectivity in
complex separations is dependent on a
delicate
balance between reagent concentrations and
pH.
Flotation where possible is carried out in an
alkaline medium, as most collectors, including
xanthates, are stable under these conditions,
and corrosion of cells, pipework etc., is
minimised

 Alkalinity is controlled by the addition of lime,

sodium carbonate (soda ash), and to a lesser
extent sodium hydroxide or ammonia. Sulphuric
or sulphurous acids are used where a decrease
in pH is required.
 These chemicals are often used in very
significant amounts in almost all flotation
operations.

 Although they are cheaper than collectors

and frothers, the overall cost is generally
higher with pH regulators per tonne of ore
treated than with any other processing
chemical.
 For example, the cost of lime in sulphide
mineral flotation is roughly double that of the
collector used, so significant operational cost
savings can be achieved by the proper choice
and use of pH regulators.

 Lime, being cheap, is very widely used to

regulate pulp alkalinity, and is used in the form
of milk of lime, a suspension of calcium
hydroxide particles in a saturated aqueous
solution.
 Lime or soda ash is often added to the slurry
prior to flotation to precipitate heavy metal
ions from solution.

 In this sense, the alkali is acting as a

"deactivator", as these heavy metal ions can
activate sphalerite and pyrite and prevent
their selective flotation from lead or copper
minerals.
 Since the heavy metal salts precipitated by
the alkali can dissociate to a limited extent
and thus allow ions into solution, cyanide is
often used with the alkali to complex them
 The role of bubble generation and froth performance

 In the science of flotation, one of the most critical

components within the process is the role of the bubbles.

 The first order rate constant (k) achieved in a variety of

industrial flotation cells of different types and sizes
operated at a range of different air rates, impeller speeds
and froth depths depended on the feed ore floatability
(P), the bubble surface area flux (Sb) generated in the cell
and the recovery across the froth phase (Rf), in a simple
numerical relationship
 Based on these findings, the performance of a
flotation unit can be considered to arise from
the interaction of a stream property- the
particle floatability (P)- with parameters that
characterise the operating conditions of the
pulp and froth zones of the unit (S b and Rf).
 In other words, the particle floatability is
governed by the degree of hydrophobicity (as
described earlier), the bubble surface area
flux is a key driver within the pulp zone of a
given cell, and the froth recovery describes
the performance across the froth zone.
 At present, there are several techniques
available to quantify the froth recovery factor,
R e . However, most of these methods are
either intrusive in the froth zone or subject to
assumptions that cannot be adopted in
conventional cell modelling
 An alternative technique for determining Rf in
industrial flotation cells was developed by
Savassi et al. (1998). A direct measurement of
Rf is achieved by solving a set of mass
balance equations with data obtained from a
sample of the concentrate and samples taken
below the pulp-froth interface.
 Entrainment

 The true flotation response has dominated

the flotation literature since the separation
process was first commercially used in 1905.
Jowett (1966) first noted the recovery of fine
particles by entrainment in water
 Johnson (1972) also showed that the degree
of entrainment was a strong function of
particle size: entrainment has been shown to
be significant below particle sizes of 50
microns.
 The engineering of flotation

 The industrial application of the flotation process

has been practised for 100 years. Although the
process is effective, industrial flotation practice
often requires several stages to produce the
product quality desired by the market.

 These stages are combined in various methods

and are referred to as "flotation circuits".
 Basic flotation circuits
 Commercial flotation is a continuous process.
Cells are arranged in series forming a bank.

 Pulp enters the first cell of the bank and gives

up some of its valuable minerals as froth; the
overflow from this cell passes to the second
cell, where more mineralised froth is removed,
and so on down the bank, until barren tailings
overflow the last cell in the bank.
 Flowsheet design

 In designing a suitable flowsheet for a

flotation plant, the primary grind size is of
major consideration.

 This is mainly due to the fact that the

flotation response depends on the level of
liberation of the minerals in the ore.
 The target grind size can be estimated based
on past experience and from mineralogical
evaluation, but laboratory grind-flotation
tests must be conducted to determine
optimum conditions.

 Grind size can be estimated knowing the size

of the grains in the ore, and grain size can be
estimated using mineral liberation analysers.
 The purpose of the primary grind is to promote
economic recovery of the valuable ore minerals.

 Batch tests are performed, utilising various

reagent combinations, on samples of ore
ground to various degrees.

 Incremental concentrate samples are weighed

and assayed, and the results plotted as
recovery-time and recovery grade curves.
 Initially, a grind size should be chosen which
gives a reasonable rougher grade and
recovery within an acceptable flotation time.
 Circuit flexibility

The decision having been reached to design a

flotation
circuit according to a certain scheme, it is
necessary to provide for fluctuations in the
flow rate of ore to the plant, both large and
small, and for minor fluctuations in grade of
incoming ore
 The simplest way of smoothing out grade
fluctuations and of providing a smooth flow
to the plant is by interposing a large storage
agitator between the grinding section and the
flotation plant:

Grind * Storage Agitator * Flotation Plant

 Any minor variations in grade and tonnage are
smoothed out by the agitator, from which material
is pumped at a controlled rate to the flotation plant.

 The agitator can also be used as a conditioning

tank, reagents being fed directly into it. It is
essential to precondition the pulp sufficiently with
the reagents before feeding to the flotation banks,
otherwise the first few cells in the bank act as an
extension of the conditioning system, and poor
recoveries result.
 Control systems can be installed to maintain the
flow rate of the slurry as constant as possible.

 The control system starts in the grinding circuit

where the feed rate of ore to the grinding mills is
maintained constant using variable speed
feeders.

 The level of slurry in pump boxes is also

maintained constant by automatically adjusting
pump speed using variable speed drives.
 Levels of slurry in flotation cells are
maintained constant by using automatic cell
level control systems.

 Provision must be made to accommodate any

major changes in flow rate which may occur;
for example, a number of mills may have to
be shut down for maintenance
 Flotation machines

 Although many different machines are

currently being manufactured and many more
have been developed and discarded in the
past, it is fair to state that two distinct groups
have arisen: pneumatic and mechanical
machines.
 Pneumatic machines either use air entrained
by turbulent pulp addition (cascade cells), or
more commonly air either blown in or
induced, in which case the air must be
dispersed either by baffles or by some form
of permeable base within the cell.

 Generally pneumatic machines give a low-

grade concentrate and little operating
trouble.
 Since air is used not only to produce the froth
and create aeration but also to maintain the
suspension and to circulate it, an excessive
amount is usually introduced and for this and
other reasons they have been little used.
 Mechanical flotation machines are the most
widely used, being characterised by a
mechanically driven impeller which agitates
the slurry and disperses the incoming air into
small bubbles.

 The machines may be self-aerating, the

depression created by the impeller inducing
the air, or "supercharged" where air is
introduced via an external blower.
 In a typical flotation bank, there are a number
of such machines in series, "cell-to cell“
machines being separated by weirs between
each impeller, whereas "open-flow" or "free-
flow“ machines allow virtually unrestricted
flow of the slurry down the bank.
 The most pronounced trend in recent years,
particularly in the flotation of base metal
ores, has been the move towards larger
capacity flotation cells, with corresponding
reduction in capital and operating costs,
particularly where automatic control is
incorporated.
 Comparison of flotation machines

 Selection of a particular type of flotation machine for a

given circuit is usually the subject of great debate and
controversy

 The main criteria in assessing cell performance are:

 metallurgical performance, i.e. Product recovery and grade

capacity in tonnes treated per unit volume

 economics, e.g. initial costs, operating and maintenance

costs.
 In addition to the above factors, less tangible
factors, such as the ease of operation and
previous experience of personnel with the
equipment, may contribute.
Flotation plant practice

The ore and pulp preparation

 It is inevitable that there will be changes in

the character of the ore being fed to a
flotation circuit. There should therefore be
means available for both observing and
adjusting for such changes.
 Variation in the crystal structure and
intergrowth may have an important effect on
liberation and optimum grind size.

 Change in the proportion of associated

minerals is a very common occurrence and
one which may be largely overcome by
blending the ore both before and after
crushing has been completed.
 When the feed is high grade it is relatively
easy to produce a highly mineralised froth
and high-grade concentrate; when it is low
grade it is harder to maintain a stable froth
and it may be necessary to switch one of the
final cleaning cells to a lower grade section if
cells and launders have suitable flexibility.
 Fluctuation in the nature and proportion of
minerals in the run-of-mine ore inevitably
occurs when ores are drawn from more than
one location, and the variation observed may be
further accentuated by partial oxidation of the
ore.

 This may occur from geological changes or

from delayed transportation of broken ore from
the stope in the mine to the processing plant.
 Oxidation also commonly occurs as a result of
overlong storage in stockpiles or ore-bins and
therefore it is necessary to determine how
prone a particular ore is to oxidation and to
ensure that the holding time is kept well below
a critical level.

 Oxidised ores are softened by lattice

decomposition and become more inert to
collector reagents and more prone to
overgrinding .
 Flotation of platinum ores

 Platinum is one of the Platinum Group Metals (PGMs),

which also include palladium, iridium, osmium,
rhodium, and ruthenium. They are generally found
together in economic ores, and 90% of PGM production
comes from South Africa, Russia and Zimbabwe.

 In 2004, 44% of platinum was used in catalysts for

motor vehicle emission control, and 33% in jewellery.
The PGMs are classed with gold and silver as precious
metals
 DEWATERING
 With few exceptions, most mineral-
separation processes involve the use of
substantial quantities of water and the final
concentrate has to be separated from a pulp
in which the water-solids ratio may be high.

 Dewatering, or solid-liquid separation,

produces a relatively dry concentrate for
shipment
 Partial dewatering is also performed at
various stages in the treatment, so as to
prepare the feed for subsequent processes.
Dewatering methods can be broadly classified
into three groups:

 (1) sedimentation;
 (2) filtration;
 (3) thermal drying
 Sedimentation is most efficient when there is a
large density difference between liquid and solid.

 This is always the case in mineral processing

where the carder liquid is water.

 Sedimentation cannot always be applied in

hydrometallurgical processes, however, because
in some cases the carrier liquid may be a high-
grade leach liquor having a density approaching
that of the solids.
 Dewatering in mineral processing is normally
a combination of the above methods

 The bulk of the water is first removed by

sedimentation, or thickening, which produces
a thickened pulp of perhaps 55-65% solids by
weight
 Up to 80% of the water can be separated at
this stage. Filtration of the thick pulp then
produces a moist filter cake of between 80
and 90% solids, which may require thermal
drying to produce a final product of about
95% solids by weight.
Sedimentation

 Rapid settling of solid particles in a liquid

produces a clarified liquid which can be
decanted, leaving a thickened slurry, which
may require further dewatering by filtration
 The settling rates of particles in a fluid are governed
by Stokes' or Newton's laws, depending on the
particle size .

 Very fine particles, of only a few microns diameter,

settle extremely slowly by gravity alone, and
centrifugal sedimentation may have to be performed.

 Alternatively, the particles may be agglomerated, or

flocculated, into relatively large lumps, called flocs,
that settle out more rapidly.
 Coagulation and flocculation

 Coagulation causes extremely fine colloidal

particles to adhere directly to each other. All
particles exert mutual attraction forces,
known as London- Van der Waals' forces,
which are effective only at very close range
 Normally, the adhesion due to these forces is
prevented by the presence around each
particle of an electrically charged
atmosphere, which generates repulsion
forces between particles approaching each
other.
 Gravity sedimentation

 Gravity sedimentation or thickening is the

most widely applied dewatering technique in
mineral processing, and it is a relatively
cheap, high capacity process, which involves
very low shear forces, thus providing good
conditions for flocculation of fine particles
 The thickener is used to increase the
concentration of the suspension by
sedimentation, accompanied by the formation
of a clear liquid.

 Thickeners may be batch or continuous units,

and consist of relatively shallow tanks from
which the clear liquid is taken off at the top,
and the thickened suspension at the bottom
Filtration

 Filtration is the process of separating solids

from liquid by means of a porous medium
which retains the solid but allows the liquid
to pass.
 TAILINGS DISPOSAL
 The disposal of mill tailings is a major
environmental problem, which is becoming more
serious with the increasing exploration for
metals and the working of lower-grade deposits.

 Apart from the visual effect on the landscape of

tailings disposal, the major ecological effect is
usually water pollution, arising from the
discharge of water contaminated with solids,
heavy metals, mill reagents, sulphur compounds,
etc.
 Waste must therefore be disposed of in both
an environmentally acceptable and, if
possible, economically viable manner.

 Disposal is governed by legislation and may

involve long-term rehabilitation of the site.
 The nature of tailings varies widely; they are
usually transported and disposed of as a slurry
of high water content, but they may be
composed of very coarse dry material, such as
the float fraction from dense medium plants.

 Due to the lower costs of mining from open

pits, ore from such locations is often of very
low grade, resulting in the production of large
amounts of very fine tailings
 Methods of disposal of tailings

 The methods used to dispose of tailings have

developed due to environmental pressures,
changing milling practice, and realisation of
profitable applications.

 Early methods included discharge of tailings into

rivers and streams, which is still practised at
some mines, and the dumping of coarse
dewatered tailings on to land.
 Tailings dams

 The design, construction, and operation of

tailings dams is a major consideration for
most new mining developments, as well as
for many existing operation.

 It is economically advantageous to site the

impoundment close to the mine, but this
imposes limits on site selection.
 The type of tailings embankment is generally
determined by:
 the local seismic activity,
 water clarification,
 tailings properties and stability,
 tailings distribution, foundation and

hydrological conditions,
 Environmental conditions
The ground underlying the dam must be
structurally sound and able to bear the
weight of the impoundment.
 If such a site cannot be found close to the

mine, it may be necessary to pump the

tailings, at a high slurry density, to a suitable
location
 The disposal of tailings adds to the
production costs, so it is essential to make
disposal as cheap as possible.
6. COAL TECHNOLOGY
 6.1 Composition and classification
 6.2 Beneficiation, cleaning briquetting
 6.3Carbonization and Tar processing
 6.4Gasification
 6.5Environmental aspects of coal utilization
COAL CHEMICALS –Historical background

 Coke was an article of commerce among the Chinese over 2000 years
ago and in the Middle Ages was used in arts for domestic purposes.
  
 1620 – the production of coke in an oven was first recorded
  
 Up until the middle of the 19th century, coal tar and coal tar products
were regarded as waste
  
 Synthesis of the first coal tar (by Sir William Perkin – 1856), caused a
great demand for coal tar, and it became a commercial product of
increasing value.
  
 In 1792, the first successful experiment involving the production of
gas from coal carried out by by William Murdick, who made it possible
to light the streets of London with gas in 1812.
Introduction
 Coke – product of the Largest tonnage from the distillation
of coal.
  
 Demand for coke usually depends on the demand for steel.
  
 Most chemicals from coal were initially obtained by

destructive distillation furnishing chiely aromatics.

  
 Coal forms the world ‘s largest reserve of concentrated raw

material from which chemicals can be extracted and

produced, and it is also a cheap source of heat and power
used for processing.
Chemicals from coal- destructive
distillation
 Coal is thermally pylrolyzed or distilled by heating without contact with air
into a variety of solid, liquid and gaseous products.
  
 The nature and amount of the product depends upon the temperatrure
used in the pyrolysisand the variety of the coal used.
  
 In ordinary practice, coke oven temeperatures are maintained above 900°C (
but may range between 500 and 1000°C)
  
 The principal product by weight is coke
  
 If a plant uses temperatures from 450 – 900, the process is termed LOW
TEMEPERATURE CARBONIZATION.
  
 If temeperatures are above 900, it is designated HIGH TEMPERATURE
CARBONIZATION.
 In low temperature carbonization the quantity
of gaseous products is small and that of liquid
products is relatively large, whereas the yield of
gaseous products is larger than the yield of
liquid products, the production of coal tar being
relatively low.
  

 NB: Low temperature carbonization produes

liquids strikingly different from those produced

by high temperature carbonization, even when
the same grade of coal is used.
 Low temperature liquids contain more tar-acis and tar
baes than high temeperatuere liquids. ( market fro low
tememperature carbonization liquids is not well
established)
  
 Major liquid products from high temperature
carbonization are – water, tar, and crude light oil. The
major gaseous products are hydrogen, methane,ethylene,
carbon dioxide, carbon monoxide, hydrogen sulphide,
ammonia and nitrogen.
  
 The products other than coke are collectively known as
coal chemicals or by products.
 THE CHEMICAL THEORY OF THE PYROLYSIS OF COAL
INDICATES THE FOLLOWING STEP-BY- STEP
DECOMPOSITION:
  
 Coal consists of largely of heterocyclic nuclei –
monomers, with alkyl chains held together by 3-
dimensional C – C groups, and includes functional
oxygen groups.
  
 As the temperature is raised, the aliphatic carbon –
carbon bonds break first. (reaction begins below
200°C)
 Carbon – Hydrogen linkages beak at or near 600°C
  
 The elimination of heterocyle complexes and prograssice
aromatization are essential reactions taking place during the
decomposition as the carbonization proceeds.
  
 The molecular weights of the intermediate products regularly
decrease as the temperature rises. Water, carbon monoxide,
hydrogen, methane and other hydrocarbons are evolved.
 Decomposition is at a maximum between 600 and 800°C. All
the above reactions vary markedly in their extent depending
on the rate of heating as well as the temperature attained.
COKING OF COAL

 The two main types of coking procedures for coal are the
beehive and the by-product.
  
 Beehive coking is the obsolete, primitive method
  
 In the by-product ovens the carefully blended coal charge

is heated on both sides so that heat travels towards the

centre and this produces shorter and more solid pieces of
coke than made in the beehive oven.
  
 Air is excluded so that no burning takes place within the

oven, the heat being supplied completely from the flues on

the sides.
BY-PRODUCT COKING

 Step – by step procedures:

 
 Coal is transferred,crushed, and screened.
  
 Coal is charged to a hot, empty oven.
  
 Coal is chemically transformed to coke and

volatiles by pyrolysis.
  
 Hot coke is pushed out of the oven, quenched and

transported.
 Condencable products of disitillilation are liquiefied and
collected in the hydraulic main.
  
 Foul gas is cooles, and tar extracted.
  
 Ammonia is removed from the gas as ammonium sulphate.
  
 Gas is cooled and subjected to benzene an toluene removal
by absorption on straw oil.
  
 Hydrogen sulphide is removed.
  
 Purified gas is metered and transferred to consumers.
Approximate Yields per Metric Tonne of Coal Carbonised
(Depending on the type of Coal and Conditions Used)
Recovery of coal chemicals
 The gaseous mixture leaving the oven is made up of permanent
gases that form the final purified coke- oven coal gas for fuel ,
along with condensable water vapour, tar, and light oils and solid
particles of coal dust, heavy hydrocarbons, and complex carbon
compounds.
  
 Significant products recoverable from the vapours include:
benzene, toluene,xylene,creosote oils,cresols, cresylic acid,
naphthalene, phenols, xylols, pyridine, quinoline, and medium
and hard pitches used for electrode binders, road tar or roofing
pitches.
  
 The gas is passed from the foul main into the primary condenser
and coolerat a temperature of about 75°C and cooled to 30°C.
 The gas gas is conducted to an exhauster which serves to compress it
 ( during the compression the temperature of the gas rises to 50°C)
  
 The gas is passed to a final tar extractor, where the tar is thrown out by
impingement against metal surfaces.
  
 On leaving the tar extractor, the gas carries about three –four fold of the
ammonia and 95% of the light oil originally present when it left the oven.
  
 The gas is led to a saturator containing a solution of 5-10% sulphuric
acid where ammonia is absorbed, and crystalline ammonium sulphate is
formed.
  
 The crystallized ammonium sulphate is removed from the bottom of the
saturator by a compressed air ejector of centrifugal pump.
 The gas leaving the satutator is at about 60°C ; is taken to the final
coolers or condeners where it is scrubbed with water until its
temperature is 25°C.(During this cooling some naphther separates and
is carried along with wastewater and recovered)
  
 The gas is passed into a light oil of benzol scrubber through which the
absorbent medium ( eg straw oil , coal tar oil) is circulated at 25°C.
  
 The straw oil is sprayed into the top of the absorption tower while the
gas flows upwards through the tower.(Most scrubbers use some form
of metal packing to increase the contacting surface area)
  
 The sraw oil is allowed to absorb 2 to 3 % of its weight of light oil, with
the removal effeiciency of about 95% of the light oil vapour in the gas.
Distillation of coal tar
 Coal tar is a mixture of many chemical compounds, mostly
aromatic which vary widely in composition.
 It is a by product of the distuctive distillation of coal.9 also a by
product of the manufacture of blast furnace coke)
  
 The end product of the distillation of coal tar is pitch.
  
 The object of the distillation is to produce a salable end
product.
  
 The product must be sharply fractioned, with a minimum of
overlapping and the process must be thermally economical, and
the furnace so designed and constructed that repairs and fuel
usage are at a minimum.
Methods of distillation
 These can be divided into three general
classifications:
 Batch still (obsolete)
 Continous still ( with a single distillation

column)
 Continous unit (using multiple colums with

reboilers
Products of distillation
 Light oils
  
 Usually comprise the cut up to 200°C.
  
 They are first crudely fractioned and agitated

at a low temeperature with concentrated

sulphuric acid, neutralized caustic soda and
redistilled, furnishing – benzene, toluene,
xylenes, light solvent naphtha
  
 Middle Oils/Creosote oils
 Generally are the fraction from 200 to 250°C
  
 Contain naphthalene, phenol, and creosols.
 The naphthalene settles out on cooling, is separated by
centrifugation, and is purified by sublimation.
  
 After the naphthalene is removed, phenol and other tar
acids are obtained by extraction with 10% caustic soda
solution and neutralization or “springing” by carbon
dioxide. These are fractionally distilled.
  
 Heavy Oils
 Represent the fraction from 250 – 300°C
  
 Anthracine Oil
 The fraction between 300-350°C.
 It is washed with various solvents to remove

phenathrene and carbazole; the remaining

solid is anthracene.
Some Important Constituents of Coal Tar