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Seminar Report
By Swarnadipta Rakshit
Roll No. 14/MM/36
Project Guide: Dr.Amit Ganguly
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Department of Metallurgical and Materials Engineering
National Institute of Technology Durgapur
CERTIFICATE
__________________
( Dr.Amit Ganguly )
Signature of Project Supervisor
______________________ _______________________
( Dr. Durbadal Mandal ) ( Dr. Barnali Maji )
Signature of Seminar Coordinator Signature of Seminar Coordinator
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Contents
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1. Overview of the pyrometallurgical extraction of
copper from sulphide ores
Copper exits in nature mostly in the form of sulphide with or without other
metallic sulphides. Oxides and oxidized ores are found only in limited
quantities. The most common minerals of copper include Chalcopyrite
(2 ), Chalcocite(2),Bornite(54 ) etc. Out of these Chalcopyrite
is the ore which is most commercially feasible for extraction. Ores which
contain 0.5 to 2 percent copper are considered satisfactory for copper extraction
by concentration followed by pyrometallurgy. In case of poorer grades the
extraction is done by Hydrometallurgical or Electrometallurgical processes.
The Flow chart in the next page (fig 1) shows the different steps that are
undertaken to produce ready to use copper from sulphide ores via the
pyrometallurgical route.
After crushing and grinding, the ore particles (average size should be about 40
microns) are subjected to concentration. The concentration method used is
usually froth floatation. Xanthates are used as collectors. After concentration,
the copper percentage in the concentrate is about 20%-30%. Depending on the
percentage of copper the concentrates are subjected to a roasting process. This
is generally employed for the concentrates which are leaner (less than 25% Cu)
and is usually skipped for the richer concentrates. Then the unroasted
concentrates and the roasted calcines(a mixture of sulphides of copper and iron,
oxides of iron and mixed sulphates of copper and iron) are subjected to
smelting. The product obtained after smelting is called matte which contains
about 45%-75% Cu. This matte is then subjected to a final coppermaking
process called converting and the product obtained is called Blister Copper
which contains about 99% copper which is subsequently fire refined and cast as
anodes for subsequent electrorefining which produces cathode copper. This
cathode copper is melted and continuously cast and we get ready to fabricate
and use copper.
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Fig 1: Flowchart depicting the pyrometallurgical extraction of copper
from sulphide ores
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2. Matte Smelting of Copper
Beneficiation of copper ores produces concentrates consisting mostly of
sulphide minerals, with small amounts of gangue oxides (Al2O3, CaO, MgO,
SiO2). Theoretically, this material could be directly reacted to produce metallic
Cu by oxidizing the sulphides to elemental copper and ferrous oxide. However,
under oxidizing conditions, Cu tends to form Cu oxide(Cu2O) as well as
metallic copper. When this happens, the Cu2O dissolves in the slag generated
during coppermaking. The large amount of iron in most copper concentrates
means that a large amount of slag would be generated. More slag means more
lost Cu. As a result, eliminating some of the iron from the concentrate before
final coppermaking is a good idea.
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Converting is oxidation of molten Cu-Fe-S matte to form molten 'blister' copper
(99% Cu). It entails oxidizing Fe and S from the matte with oxygen-enriched air
or air 'blast'. It is mostly done in the Peirce-Smith converter, which blows the
blast into molten matte through submerged tuyeres. The main raw material for
converting is molten Cu-Fe-S matte from smelting.Other raw materials include
silica flux, air and industrial oxygen. Several Cu bearing materials are recycled
to the converter - mainly solidified Cu-bearing reverts and copper scrap.
The products of converting are:
(a) molten blister copper which is sent to fire- and electrorefining.
(b) molten iron-silicate slag which is sent to Cu recovery, then discard
(c) SO2-bearing offgas which is sent to cooling, dust removal and sulphuric acid
manufacturing. The heat for converting is supplied entirely by Fe and S
oxidation i.e, the process is autothermal.
The overall converting process may be described by the schematic reaction:
Fig 3: Charging, blowing and skimming in an industrial pierce smith converter. Note the hood for
collecting off-gas during blowing. Also note the leakage of off-gas during charging and skimming.
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The copper is poured from the converter into ladles and craned molten to a fire
refining furnace for S and O removal and casting of anodes. A start-to-finish
converting cycle is 6 to 12 hours. The molten blister copper obtained is about
99% Cu while the slag contains 4-8% Cu.
But there are certain limitations of this batch converting process due to which
engineers came up with the concept of continuous coppermaking. They are:-
It leaks SO2 bearing gas into the workplace during charging and pouring.
it leaks air into its offgas between its mouth and gas-collection hood,
producing a relatively weak SO2 gas.
This SO2 gas is too weak for economic recovery of sulphur.
It operates batchwise, giving uneven flow of SO2 offgas into the sulphuric
acid plant.
Automation or Computer control of such a batch process is difficult.
4. Continuous Coppermaking
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5. Concept of Direct-to-copper single furnace
smelting
It has long been the goal of metallurgical engineers to combine the two steps of
Smelting and Converting into one continuous direct-to-copper smelting process.
Fig.4 is a sketch of the ideal direct-to-copper process. The principal inputs to
the process are: concentrate, oxygen, air, flux and recycles.The principal
outputs are: molten copper, low-Cu slag, high-SO2 offgas.
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But what made Noranda discard this Direct-to- copper smelting
process? And why do the Glowgow and Olympic Dam plants treat
Chalcocite-Bornite concentrates and not Chalcopyrite?Is the process
really that efficient? Let us have a look at the typical products
obtained from a Direct-to-copper smelting furnace.
We can see that the slag contains as high as 24% copper. It arises
because there is no permanent layer of Cu2S in the furnace to reduce
Cu2O to metallic copper. The Glogow and Olympic Dam furnaces are
operated with 02/concentrate ratios which are high enough to avoid
forming a Cu2S layer. This is done to avoid the possibility of foaming
slag out the top of the furnace.
Although,it has effectively isolated SO2 offgas in one single furnace
and a continuous supply of SO2 to the sulphuric acid plant has been
maintained. But, the copper loss in slag as Cu2O is reported to be too
high in comparison to the conventional smelting+ converting
process.As high as 24% Cu is lost in slag whereas in the conventional
process only 1-2% during smelting and about 6% Cu during
converting is lost.This rich oxidised slag needs to be reduced by
metallurgical coke in an electric furnace and hence the objectives of
continuous coppermaking are not satisfied as there is extra energy
consumption.Also metallurgical grade coal is not readily available in
many countries.
Balancing these factors, it appears that direct-to-copper smelting is
best suited for Chalcocite (2 ) and Bornite(5 4 ) concentrates.
These concentrates produce little slag so that Cu recovery from slag is
not too costly. It is however not suitable for most chalcopyrite
concentrates, (about30% Cu). These concentrates produce about 2
tonnes of slag per tonne of Cu so that the energy and cost of
recovering Cu from their slag is considerable.
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6. The Mitsubishi Continuous Smelting/Converting
Process
6.1 Introduction
The Cu-in-slag problem and the significant potential benefits of
continuous processing have led to the development of continuous
coppermaking in connected smelting, slag cleaning and converting
furnaces. The potential benefits are:
(a) ability to smelt all concentrates, including CuFeS2 concentrates.
(b) elimination of Peirce-Smith converting with its SO2 collection and
air infiltration difficulties.
(c) continuous production of high S02-strength offgas, albeit from
two sources.
(d) relatively simple Cu-from-slag recovery.
(e) minimal materials handling.
The most advanced industrial manifestation of continuous
smelting/converting is the Mitsubishi process with four systems
operating in 2002 (Goto and Hayashi,1998; Ajima et af., 1999).
The First commercial application began at Mitsubishi Materials
Corporation,Naoshima,Japan in 1991 with a capacity of 270,000
tpy In 2005 it came to India when Hindalco Birla Copper
established a new Mitsubishi Process line at Dahej,Gujarat with a
capacity of 250,000 tpy copper, in addition to their conventional flash
smelter + PS converters line and Ausmelt smelter and converter line.
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6.2 The Process
Fig 5: Mitsubishi process flowsheet and vertical layout at Gresik, Indonesia (Ajima et al.,
1999). Note the continuous gravity flow of liquids between furnaces. The smelting furnace is
about 15m higher than the Hazelett caster.
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Its slag (0.7-0.9%Cu) flows continuously to water granulation and
sale or stockpile.The converting furnace blows oxygen-enriched air,
CaCO3, flux and granulated converter slag 'coolant' into the matte via
vertical lances. It oxidizes the matte's Fe and S to make molten
copper. The copper continuously exits the furnace into one of two
holding furnaces for subsequent fire- and electrorefining. The
slag(14% Cu) flows continuously into a water granulation system.
The resulting slag granules are recycled to the smelting furnace for Cu
recovery and the converting furnace for temperature control. A major
advantage of the process is its effectiveness in capturing SO2. It
produces two continuous strong SO2 streams, which are combined to
make excellent feed gas for sulfuric acid or liquid SO2 manufacture.
Also, the absence of crane-and-ladle transport of molten material
minimizes workplace emissions. These environmental advantages
plus recent improvements in productivity make the Mitsubishi process
well worth examining for new copper smelting projects.
Fig 6: Top view and front view of a smelting furnace. The refractories used are magnesite-
chrome.
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The velocities of solids and gas leaving Mitsubishi smelting furnace
lances are 130-150 m/second (Goto and Hayashi, 1998). Times of
flight of the particles across the 0.7 m distance between lance tip and
melt surface are, therefore, on the order of 10-3 to 10-2 seconds. The
temperature rise of the gas solid jet during this time is calculated to be
-50C. This is not enough to cause ignition of the concentrate.
Consequently, melting and oxidation of concentrate particles occurs
entirely after entry into the gas-slag-matte foam and emulsion beneath
the lances (Goto and Hayashi, 1998; Asaki et al., 2001). Industrial
evidence indicates that the smelting furnace contains mainly
matte(1.2- 1.5 m deep) with a gas/slag/matte foademulsion beneath
the lances (Goto and Echigoya, 1980, Shibasaki and Hayashi, 1991).
Away from the lances,SO2 & N2 gas disengages from the foam and
the matte and slag begin to separate. Newly formed slag (-0.05 m
thick and containing some entrained matte) flows towards the taphole
where it overflows. Matte also continuously overflows as new matte
is made under the lances.
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The electric slag cleaning furnace accepts molten matte and slag from
the smelting furnace. These liquids separate and form two layers in
the furnace a bottom layer of matte 0.5 - 0.8 m thick, and a top layer
of slag -0.5 m thick. The residence times of the liquids are 1 or 2
hours. These times, plus electromagnetic stirring in the furnace allows
the slag and matte to approach equilibrium. Passage of electricity
through the slag ensures that the slag is hot and fluid. This, in turn,
creates conditions for efficient settling of matte droplets from the slag.
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The slag is the main route of Cu loss from the smelter. It is important,
therefore, that the total amount of Cu-in-slag be minimized. This is
done by:
(a) maximizing slag residence time in the electric furnace (to
maximize matte settling)
(b) keeping the slag hot, fluid and quiescent
(c) minimizing slag mass (per tonne of Cu) by smelting high Cu
grade
(d) concentrates and minimizing fluxing
(e) optimizing slag composition to minimize slag viscosity and
density
6.5. The converting furnace details
The converting furnace continuously receives matte from the electric
slag cleaning furnace. It blows oxygen-enriched air blast (30-35
volume% O2), CaCO3 flux and converter slag granules onto the
surface of the matte. It also receives considerable copper scrap
including scrap anodes.
It produces:
(a) molten copper, about 0.7% S
(b) molten slag, 14% Cu
(c) SO2 bearing offgas, 25-30 volume% S02.
The molten copper continuously departs the furnace through a siphon
and launder into one of two anode furnaces, Fig 8. The slag
continuously overflows into a water-granulation system. The offgas is
drawn through a large uptake, waste heat boiler, electrostatic
precipitators and a wet gas cleaning system before being pushed into a
sulfuric acid or liquid SO2 plant. The smelting and converting
offgases are combined prior to entering the electrostatic precipitators.
The oxygen-enriched air and solids are introduced into the furnace
through 10 lances like the smelting furnace lances. The tips of the
outside pipes are 0.3 to 0.8 m above the bath - the inside pipe tips
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above or just through the roof. The outer pipes are continuously
rotated to prevent them from sticking to their roof collars. They are
also slowly slipped downwards as they burn back.
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A unique feature of Mitsubishi converting is its CaO-based (rather
than SiO2 based) slag (Yazawa et al., 1981; Goto and Hayashi, 1998).
Early in the development of the process, it was found that blowing
strong O2 'blast' onto the surface of SiO2-based slag made a crust of
solid magnetite. This made further converting impossible. CaO, on
the other hand, reacts with solid magnetite, molten Cu and O2 to form
a liquid CaO-Cu2O-FeO, slag.The slag typically contains: 12- 16% Cu
(-60% as Cu20, balance Cu),40-55% Fe (about 70% as Fe+++,balance
Fe++) and 15-20% CaO.Its viscosity is about 10-1 kg/m.s (Wright et
al., 2000).
Mitsubishi copper contains more Sulphur than Peirce-Smith
converter copper, about 0.7% vs. about 0.02% in Pierce-Smith
converter. The only disadvantage of this is a longer oxidation period
in the anode furnace. The S content can be lowered in the Mitsubishi
converter by supplying more O2 but this increases the amount of Cu in
slag. 0.7% - 0.8% S in copper seems optimum.
The reactions taking place during the converting process are as
follows:
(a) Matte flows continuously into the furnace and spreads out on the
furnaces permanent layer of molten copper.
(b) it reacts with O2 under the lances to make FeO and molten copper
by the reactions:
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(d) Cu20, FeO and Fe304 are slagged by the reactions:
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6.6. Optimum Matte Grade
The Cu grade of the matte being produced by the smelting furnace
(and flowing into the converting furnace) is chosen as a balance
between:
(a)the amount of Cu lost in the discard slag from the electric furnace.
(b) the amount of granulated high-Cu slag which must be recycled
back from the converting furnace to the smelting furnace
(c) the amount of coal which must be added to the smelting furnace
and the amount of coolant which must be added to the converting
furnace.
The optimum matte grade for the Mitsubishi process is 68% Cu.
With this matte grade, the discard slag from the electric slag cleaning
furnace contains 0.7-0.9% Cu and converter slag recycle is 0.1 to 0.3
tonnes per tonne of concentrate feed.
6.8. Limitations
Apart from the myriad advantages,the Mitsubishi process does suffer
from few limitations like:
The three furnace concept maximises heat losses which does not
satisfy the minimum energy consumption criteria of continuous
coppermaking.
Further movement of molten materials from furnace to furnace
results in fugitive emission of SO2 gas. This SO2 gas gets
directly released to the atmosphere and hence pollutes it.
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6.9. Conclusion
Hence it can be concluded that although the Mitsubishi process has
reached close to the ideal continuous coppermaking but the above
limitations show that it is not the ultimate.Hence much work is left for
us,the budding metallurgical engineers to devise a process that is
more efficient and sustainable than the Mitsubishi process.
7. Acknowledgement
I would like to thank my project guide Dr.Amit Ganguly for giving
me an opportunity to know more about the extractive metallurgy of
copper and its industrial manifestations.I would also like to thank
Dr.Durbadal Mandal and Dr.Barnali Maji for giving me an
opportunity to present a seminar in front of eminent professors.
8. References
Extractive Metallurgy of Copper by W.G Davenport,
M. King, M.Schlesinger and A.K Biswas.
Goto, M. and Hayashi, M. (1998) The Mitsubishi
Continuous Process - A Description and Detailed
Comparison Between Commercial Practice and
Metallurgical Theory,Mitsubishi Materials
Corporation, Tokyo, Japan.
Extraction of Nonferrous Metals by H.S Ray,R
Sridhar and K.P Abraham.
Continuous process for copper smelting and
converting in a single furnace by oxygen injection by
John C. Yannopoulos,Westport,Conn,Newmont
Mining Corporation,New York,N.Y
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