ENVIRONMENTAL CONSIDERATIONS FOR PYROMETALLURGICAL PROCESSES

1. BACKGROUND

 Control of pollutants from metallurgical processing has long been a

troublesome and expensive problem and one that has been increasing in
importance over recent years
 Greater emphasis has been put on minimizing contamination, and higher
standards of control on permissible air and water pollutants are now being
set by strict legislation in many countries
 Of concern has been SO2 and greenhouse emissions especially from
pyrometallurgical processes
 As early as 1860s SO2 was being captured as sulphuric acid and nearly 40%
of the total sulphur to the smelter was being captured this way
 The remaining SO2 gas was sent up through tall stacks to be dissipated
before coming back to the ground
 The process gas from these pyrometallurgical processes contain solid
particulate matter which can be removed by various types of dust collectors,
and gaseous chemical compunds of which SO2 is by far the most common
one
 Other gases such as chlorine, NOx, HCl gas are also by-products of some
operations
 Various methods of chemical combinations can remove these gaseous
products
 Besides gaseous emissions a lot of solid waste materials material such as
slag is generated as a results of these processes
 These solids may contain harmful elements such as heavy metals which may
get released into the environment

2. WHY CLEAN THE GAS?

There are several reasons for cleaning gases from metallurgical processing. The
most important of these are as follows:

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1. to recover value bearing particulate material which can be returned to the
plant for reprocessing; for e.g. a Cu smelter treating less 75µm might lose as
high as 8% of the input tonnage as flue dust; if this is not recovered and
recycled it would greatly affect the economics of the overall process
2. environmental pollution, both from the view point of workers exposed to
harmful gas emissions in dangerous concentration and such gases as SO2
which can cause agricultural damage by combining with water vapour in the
atmosphere to form sulphurous and sulphuric acid and burn leaf crops
3. to remove value bearing gaseous by products such SO2, which can be used
as feed material for the production of marketable sulphuric acid or
elemental sulphur
4. to clean high calorific product gas containing high percentages of
combustible CO that having been freed of contained particulate matter can
be piped and through burners through burners, without dangers of
plugging, and be used wherever required as a fuel gas throughout the plant
5. Many metallurgical gases are the product of high temperature furnace
operations and leave the process carrying a high content of sensible heat.
This heat can be recovered in such devices as waste heat boilers and
recuperative systems before the cooled gas is permitted to escape to the
atmosphere

3. DUST COLLECTORS: REMOVAL OF PARTICULATE MATTER FROM GASES

 Dust collection is done by a variety of methods, with the method chosen

taking into account
a) the size of the particles to be removed
b) the temperature of the gas
c) the gas volume
d) the gas velocity
e) whether the collector is to be used alone or as part of a series, and
f) whether sensible heat in the gas is to be removed or not
 particle sizes and types are broken into four categories
o Fume  0.05 to 1 micron, fine, solid particles formed by the
condensation of metal vapours
o Dust  1.0 to 50 micron, small, solid particles formed from the of
large particles

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 o Mist  0.5 to 10 micron, liquid droplets generated by condensation
o Smoke  0.05 to 1.0 micron, fine solid particles resulting from
incomplete combustion of organic materials
 Dust loading are given in grains per cubic feet or grams per cubic meter (1.0
grain per cubic foot=2.3 grams per cubic metre; 1 grain = 0.065gram)

There are four designations of dust loadings:

o Light  ½ to 2 grains per cubic foot (1.15 to 4.6 grams per cubic
metre)
o Medium  2 to 3 grains per cubic foot (4.6 to 6.9 grams per m3)
o Moderate  3 to 5 grains per cubic foot (6.9 to 11.5grams per m3)
o Heavy  >5 grains per cubic foot (> 11.5 grams per m3)

There are 8 types of dust collectors in common usage, each of which has its
best collector efficiency within a certain particles size range. The collector types
and their efficiency ranges are as follows:

 Settling Chamber  90% efficient above 50 microns

 Cyclone  70 microns 20% efficiency; 100microns 92% efficiency
 Multiclone  3 microns 20% efficiency; 70 microns 99% efficiency
 Bag House  range 0.5 to 100 microns 99% efficiency
 Spray Tower  10 microns 88% efficiency, 90 microns 98% efficiency
 Venturi scrubber  0.2 micron 30% efficiency, 5 microns +99% efficiency
 Electrostatic Precipitator  0.1micron 82% efficiency, 2microns +99%
efficiency
 Wet scrubber  0.3 micron 20% efficiency, 9 microns 99% efficiency

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Comparative particle size ranges and corresponding applicable collecting equipment

Comparative particle size collector efficiencies

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Settling Chamber

 One of the oldest and simplest method for dust collection and is used to remove the
coarser particles above 50 microns
 Works on the principle of a small flue carrying gas entering a much larger chamber with a
great increased cross sectional area
 The gas velocity drops due to the larger chamber volume, and as the reduced velocity is
no longer able to carry along the larger dust particles in the gas stream, they drop out
 A small discharge flue carries away the cleaned gas
 Gas temperature is not important as the chamber is of steel construction and can be
lined with heat resistant fire bricks
 Simple construction with no mechanical parts to wear out rapidly and can be made quite
large to handle high volume gas throughput

Clean gas
Gas In

Settled solids

Cyclones

 Type of collector with no moving parts that are used dry and conserve sensible heat in
hot gases passing through them
 Best at treating medium sized particles, having an efficiency of 20% recovery on 7micron
particles, and increasing to 92% for with larger particles, 100micron
 It’s a low cost collector, inexpensive to operate, and relatively small in size
 Most commonly used type of collector
 Principle of operation is that a high velocity gas stream enters near the top cylindrical
section of the cyclone and impinges tangentially on the curved surface
 Centrifugal force resulting from the tangential velocity of the gas carries the dust
particles to the wall of the cyclone, where they slide downward due to gravity and are
led out through a cone shaped bottom section
 A discharge opening at the top of the collector carries off the cleaned gas

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 If there is excessive scouring and wear on the steel cyclone shell from sand blasting
effect of fine dust particles entering the unit at high velocity, this wear can be controlled
by inserting porcelain lining in the cylindrical feeding section of the cyclone
 Can be used alone as a primary unit or as an intermediate collector if used as one unit in
series

Multiclones

 Are a form of cyclone collectors, also used dry, where several small diameter cyclones
are combined together inside a single container shell and operated collectively as one
unit
 Takes advantage of the greater operating efficiency of small diameter cyclones,
 because the small cyclones are splitting the gas dust load and operating in parallel, the
several cyclones in multiclone can accommodate an overall large gas volume that has a
heavy dust loading with quite high overall cleaning efficiency

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Bag Houses

 are filter type collectors and are one of the oldest, most reliable types still in widespread
general use
 gas containing particulate matter is blown into the interior of fabric bags, whereupon the
gas passes on through the fabric and out of the collector and leaves behind the solids,
dust, or fume that are retained by the fabric
 after the first brief instant the filering action is actually being done by the dust cake that
has deposited on the fabric filter, rather than by the size of weave in the fabric bag itself
 periodically the bags, which are used in large groups in a bag house, are shaken, or the
flow of gas is momentarily reversed to shake or blow off the particle layer that has
collected inside the bags
 this dust falls down into a hopper at the bottom of the bag house and removed
 bag life is from 6 months to 2 years
 a torn bag must be replaced immediately as it will leak and not filter
 used over wide range of particle sizes, 0.05 to 100 micron with efficiency of up to 99%,
but is generally considered best as a collector for smaller sized particles and gases with a
light to medium dust loading
 can be used alone or as a single unit for conditions where particle sizes are small and
dust loadings or gas volumes are not excessive

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Spray Towers

 utilize particle collection by fine water droplets, with the drops of the water contacting
the solid particles in the gas stream and carrying them out of it
 in its simplest form the spray tower has a downward flow of atomised water droplets
sprayed from nozzles to completely fill the interior of the tower, and rising through this
spray is an upward flow of dirt gas to be cleaned
 solids carried to the bottom of the tower by water droplets and are drained from here to
be de-watered and recovered
 spray jets are available for a variety of spray shapes to fill the tower interior to give the
required fineness of water droplets and to supply the volume of water required
 for maximum efficiency these gases should match the dust particle size, the gas volume
and the gas velocity through the tower
 particles of all sizes can be removed, but finer sizes below 1 micron are more difficult
 it is comparatively simple, inexpensive type of collector that can handle large gas
volumes with all degrees of dust loading
 as it is a wet type collector gas passing through the tower is cooled and sensible heat lost

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VENTURI SCRUBBERS

 are wet type gas cleaning device in which dirty gas and water for cleaning are atomised
in a moving gas stream
 relative velocity between gas and water droplets very high
 gas velocity is in the range 3500 to 7500m/min, and this promotes large treatment
capacity
 very cheap, simple and is very efficient for small-sized particles, +99% for 5micron size,
and can handle large gas capacities in a quite small unit because of its rapid rate of
treatment
 wet process, therefore any sensible heat is lost

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ELECTROSTATIC PRECIPITATOR (in Assignment)

WET SCRUBBER (in Assignment )

GAS CLEANING-REMOVAL OF CONTAMINATING COMPOUNDS FROM GASES

Sulphur Dioxide

 most common gas compound found in product gases from metallurgical treatment
 this is due to the fact that sulphide ores are the form in which many of the common non-
ferrous metals are found and their processes include roasting, smelting, & converting, all
of which are oxidizing operations that produce large quantities of SO2
 SO2 has long been considered an undesirable pollutant in the atmosphere because of
human respiratory and agricultural damage
 Because of stricter clean air standards being legislated by many countries to control
smelter emissions, the removal of SO2 from metallurgical process gases is of great
importance
 There are three methods of treating gases containing SO2 to remove sulphur

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 o convert the SO2 to sulphuric acid by the contact process,
o sulphur can be extracted in the form of elemental sulphur, and
o SO2 can be combined with calcium oxide to form calcium sulphite and calcium
sulphate

Contact Acid Process

 works best and most economically on gases containing at least 3.5%SO 2 and preferably
10 to 14% SO2
 acid strength produced varies from plant to plant but is usually in the range 98 to 99.6%
H2SO4, which is normally diluted with water to 93% H 2SO4, the usual commercial market
strength
 hot smelter gas must first be cooled and cleaned to prevent contamination during
processing, and it is particularly important to eliminate any impurities such as As2O3,
which forms during roasting of As containing materials
 hot process gas first passed through a waste heat boiler to recover sensible heat and
then to an electrostatic precipitator to remove particulate matter
 if dust content is very high, a cyclone can be installed ahead of the precipitator
 cleaned gas is now passed through a water scrubbing tower to wash it, followed by a
refrigeration cooler to lower the temperature below dew point
 a wet precipitator removes the mist formed in the cooling cycle and any dust which is
remaining after the initial dust removal treatment
 SO2 is catalytically oxidised to trioxide by atmospheric oxygen

2SO2 + O2  2SO3

 with oxidation taking place on the surface of the catalyst at atmospheric

 SO3 gas, on cooling, is sent to an absorption tower where SO 3 is absorbed in circulating
98.5%H2SO4 (which gives optimum absorption efficiency)
 SO3 combines with water in the acid to produce 99.6%H2SO4:
SO3 + H2O  H2SO4
 tail gases leaving the absorption tower contain H2SO4 mist, and also ~0.1-0.2% SO2
 scrubbing thse gases with lime solution precipitates the sulphur as calcium sulphite or
calcium sulphate and a wet electrostatic precipitator will remove both these and any
H2SO4 mist before the gas is finally released from a stack
 final released gas has less than 0.01%SO 2, and over 99% of the SO2 in the acid plant input
gas has been removed

Elemental Sulphur

 can be used to treat high SO2 smelter gases particularly those containing over 10% SO2

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 elemental sulphur has fine, long term storage characteristic and is adaptable to other
different uses than sulphuric acid
 process gas is first cooled, cleaned and dried in a similar manner to that used in the
contact acid process
 it is the reduced with carbon (natural gas or coal) or hydrogen at 500oC

SO2 + C  CO2 + S(g)

SO2 + H2  H2O + S(g)

 a mixture of SO2 and air is passed continuously through furnace and resulting gases are
condensed to 170oC to liquid elemental sulphur, which is tapped from the condenser
and cast into blocks
 gas passing from this condenser still contains some SO 2, so it is reheated to 240 oC and
reacted with hygrogen sulphide

2H2S + SO2  2H2O + 3/2 S2 (g)

 which is again condensed to liquid, tapped and cast

Wet Scrubbing by Fume Calcium Oxide (or Limestone)

 Wet scrubbing by fume calcium oxide or limestone of off-gases containing small amounts
of SO2 has been carried out where SO 2 concentration is too low for reasonable treatment
for either H2SO4 or elemental sulphur production
 Also used to further clean tail gas from contact acid plants prior to its final discharge to
the atmosphere
 Spray towers and venture scrubbers are used with water solid slurries of both fine CaO
and CaCO3
 The following reactions occur

SO2 + CaO  CaSO3

 and to some extent

CaSO3 + ½ O2  CaSO4

 The solids are removed by settling tanks, venture scrubbers and centrifuges to be
discharge to a disposal site, while the cleaned gas is released from a stack
 process more efficient on lower concentrations of SO2 and decreases in percent removal
as amount of SO2 in the feed gas increases

GAS DISSIPATION FROM TALL STACKS

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 even the most efficient dust collecting system or chemical treatment processes does not
remove all of the pollutants in a gas
 there is always a small amount of contaminant that has to be released finally to the
atmosphere
 there are also conditions where SO2 is too low to be efficiently removed as H 2SO4 or
elemental sulphur or where the smelter is located in a remote area where there is no
market within shipping rang for the H2SO4
 there are also smelters in areas where there are low population densities and little
agriculture to be damaged by SO2 discharge
 in all these cases the solution has been to disperse the pollutants from tall stacks so that
both particulate matter and SO2 are widely scattered and diluted before they reach the
ground and no longer at level of harmful concentrations
 the tendency has been to build taller and taller stacks to put the gases to put the gases
with their pollutants out into the upper air currents and increase probability of
dispersion over a large area to ensure the greatest dilution of contaminants

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HEAT RECOVERY

 gases from pyrometallurgical processes are at elevated temperatures, some quite high, and
contain an appreciable amount of sensible heat which is commonly recovered and used
before the gas is allowed to pass on to pollution control treatment

 in some gas cleaning operations, such as electrostatic precipitators & bag houses, where
temperature is a limiting factor, the cooling of the gas is an integral part of the overall
processing and an additional reason for removal of the sensible heat

 heat removal is often done in heat exchangers or waste heat boilers, which are similar in
design

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