Non-Ferrous Extractive Metallurgy
Non-Ferrous Extractive Metallurgy
on
NON-FERROUS EXTRACTIVE METALLURGY
(MM - 15035)
B.Tech, 6th Semester (Metallurgy & Materials Engineering)
Course Coordinators
1. Dinesh Kumar Mishra
Email id: [email protected]
2. Gautam Behera
Email id: [email protected]
This document does not claim any originality and cannot be used as a substitute for prescribed textbooks. The
information presented here is merely a collection by the faculty members (Course Coordinators) for their
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specifically disclaim any implied warranties of merchantability or fitness for a particular purpose.
CONTENTS
1. Introduction to Non-Ferrous Metal Extraction 01-16
1.1 General Principles of Extraction of Metals from Oxides and Sulphides 01
1.2 Mineral Resources of Non-ferrous Metals in India 12
1
Chapter 1 Introduction to Non-Ferrous Metal Extraction
In metal extraction, a vast majority of metallurgical reactions are made to take place at
elevated temperatures because then the ore compounds become relatively unstable, facilitating the
release of the metal. This is the basis of pyrometallurgy, in electrometallurgy, the dissociation or
decomposition of a compound in solution (i. e. reduction of an iron) is brought about to employing
electric forces. In hydrometallurgy, the reduction process depends on the judicious manipulation of
the chemical reaction taking place in an aqueous solution.
The process of extracting the metals from their ores and refining them is called
metallurgy. The choice of the process depends upon the nature of the ore and the type of the
metal. The metal content in the ore can vary depending upon the impurities present and
chemical composition of the ore. Some common steps involved in the extraction of metals
from their ores are:
i. Crushing and pulverization
ii. Concentration or dressing of the ore
iii. Calcination and roasting of the ore
iv. Reduction of metal oxides to free metal
v. Purification and refining of metal
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
The crushed pieces of the ore are then pulverized (powdered) in a stamp mill shown
in (Fig. 1.2). The heavy stamp rises and falls on a hard die to powder the ore. The powdered
ore is then taken out through a screen by a stream of water. Pulverization can also be carried
out in a ball mill. The crushed ore is taken in a steel cylinder containing iron balls. The
cylinder is set into revolving motion. The striking balls pulverize the crushed ore into fine
powder.
3
Chapter 1 Introduction to Non-Ferrous Metal Extraction
or Copper Pyrites CuFeS2. It is based on the different wetting properties of the surface of the ore
and gangue particles.
4
Chapter 1 Introduction to Non-Ferrous Metal Extraction
The sulphide ore particles are wetted preferentially by oil and gangue particles by
water. In this process, finely powdered ore is mixed with either pine oil or eucalyptus oil. It is
then mixed with water. Air is blown through the mixture with a great force. Froth is produced
in this process which carries the wetted ore upwards with it. Impurities (gangue particles) are
left in water and sink to the bottom from which these are drawn off (Fig. 1.5).
contaminated with iron (III) oxide Fe2O3, titanium (IV) oxide TiO2and silica SiO2 . These
impurities are removed by digesting the powdered ore with aqueous solution of sodium hydroxide at
420 K under pressure. Aluminium oxide dissolves in sodium hydroxide, whereas, iron (III) oxide,
silica and titanium (IV) oxide remain insoluble and are removed by filtration.
Reaction 1.1:
Sodium aluminate (Na3AlO3) is diluted with water to obtain precipitate of aluminium
hydroxide. It is filtered and ignited to obtain pure alumina.
Reaction 1.2: ( )
Reaction 1.3: ( )
5
Chapter 1 Introduction to Non-Ferrous Metal Extraction
6
Chapter 1 Introduction to Non-Ferrous Metal Extraction
Acidic Flux:
SiO2 is used as acidic flux to remove basic impurity of FeO in metallurgy of Cu.
Reaction 1.18:
(Acidic flux) (Basic gangue) (Slag)
The fusible slag, such as calcium silicate formed during smelting floats over the
molten metal and is thus easily removed. Another advantage is that the slag provides a
covering to the molten metal thus preventing it from getting oxidized by air.
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
(iii) Self-reduction:
This is applied to the sulphide ores of copper, mercury and lead. The ores are
heated in air, a part of these sulphide ores is changed into the oxide or sulphate which then
reacts with the remaining part of the sulphide ore to give the metal and Sulpher dioxide. The
reactions showing their extraction are given below:
Reaction 1.24:
Copper glance
Reaction 1.25:
Copper produced at this stage is called Blister copper. The evolution of Sulpher
dioxide produces blisters on the surface of solidified copper metal.
Reaction 1.26:
Cinnabar
Reaction 1.27:
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
Reaction 1.28:
Galena
Reaction 1.29:
Reaction 1.30:
Reaction 1.31:
This solution is decanted off and treated with zinc to precipitate silver,
Reaction 1.33: [ ( ) ] [ ( ) ] ( )
(ii) Electrolytic Reduction:
Active metals like sodium, potassium and aluminium etc., are extracted by the
electrolysis of their fused (molten) salts. For example, sodium is obtained by the electrolysis
of fused sodium chloride (Down's process). The reactions taking place in the electrolytic cell
are:
Reaction 1.34:
Na+ ions move towards the cathode and Cl- ions move towards the anode.
Following reactions take place at the electrodes:
Reaction 1.35 (At Cathode): (Reduction)
(Negative electrode) (metal)
Reaction 1.37:
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
10
Chapter 1 Introduction to Non-Ferrous Metal Extraction
For example, in the electrolytic refining of crude copper (blister copper), a large piece
of impure copper is made anode and a thin piece of pure copper is made the cathode. An
acidified solution of copper sulphate is used as an electrolyte. On passing an electric current
11
Chapter 1 Introduction to Non-Ferrous Metal Extraction
of low voltage through the solution copper (II) ions obtained from copper sulphate solution
go to the cathode where they are reduced to the free copper metal and get deposited.
Reaction 1.40 (At Cathode): (Reduction)
(Negative electrode) (metal)
An equivalent amount of the metal from the anode dissolves into the electrolyte as
Cu+2 ions.
Reaction 1.41 (At Anode): (Oxidation)
(Positive electrode)
As the process goes on, anode becomes thinner while the cathode becomes thicker.
The impurities like silver, gold settle down at the bottom of the cell as 'anode mud'.
The minerals of the 1 st category, if properly exploited can not only meet the domestic
demand but can also yield a surplus for export. Although the minerals in the 2 nd category are
insufficient to meet the growing domestic demand, they should be fully exploited. The 3 rd
category resources are at present inadequate for commercial exploitation.
From the above three categories India is deficient in some of the common metals such
as Cu, Zn, Pb, Sn, Co, and Ni, it reserves of Fe, Mn, Mg, Al, and Ti are expensive. Further,
India has abundant reserves of strategically important metals namely Th, Zr, and Be. We now
discuss the mineral resources of individual elements.
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
Aluminium (Al): According to reliable sources, the East Coast of India has one of the
world’s largest deposits of bauxite. Since this deposit is rich in gibbsite and has low content
in silica and titania, it is ideal for Bayer process for the extraction of alumina. Currently,
India has an installed capacity of 320,000 tons for aluminium products, which is adequate to
meet the present demand. Das Gupta (1979) has predicted that after 1990, the whole Europe,
including the U.S.S.R., will have to rely largely of Africa and India for obtaining bauxite and
alumina.
Antimony (Sb): Commercially exploitable deposits of antimony have been so far located in
India, although small deposits of antimony ores have been found in Lahaul and Spiti
(Himachal Pradesh). At present, the entire annual requirement, i.e. 500-700 tons, is being met
by importing the metal, its ores, and concentrates.
Beryllium (Be): Berly, the chief ore of Be, occurs in pigmatites which is associated with
grantes and is found in Rajasthan, Tamil Nadu, Jammu and Kasmir, and Bihar. At one time,
almost the entire beryl output of India was being exported but the Atomic Energy
Establishment (AEE) now handles its production and sale. Although beryllium is not
produced on a commercial basis in India, substantial groundwork has been done at Bhabha
Atomic Research Centre (BARC), Bombey, in beryllium production technology.
Chromium (Cr): The principal chromite deposits of India are located in Singhbhum district
(Bihar), Karnataka, Krishna and Sawantwadi (Maharashtra), and Keonjhar district (Odisha).
The chromite reserves of India, although estimated to be limited to about 17 million tons,
should be able to meet the domestic requirement for a long period, and a production of
10,000 tons per annum can be sustained for years.
Nickel (Ni) and Cobalt (Co): The Cu ore belt passing through Singhbhum (Bihar) contains
also a Ni ore body which may provide 1000 tons of nickel annually. In fact, India’s nickel
reserves are about 100 million tons, of which 6.5 million tons, averaging 0.85 % nickel, are
located at Sukinada (Odisha). Ni has also been found associated, in very minute quantities,
with the gold-quartz reefs at Kolar (Karnataka) and uranium ores at Jaduguda (Bihar). The
traces of Co have been found along with Cu ores of Khetri and Mn ores of Kalahandi
(Odisha).
Cadmium (Cd): Cadmium is recovered as a byproduct from the zinc smelters at Debari
(Rajasthan), Vishakhapatnam (Andhra Pradesh), and Alwaye (Kerala). Indigenous sources
meet most of the domestic cadmium requirements.
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
Copper (Cu): About 90% of reserves are spread over Bihar, Rajasthan, and Madhya Pradesh,
the most important deposits being located in the Singhbhum copper belt in Bihar. At present,
Hindustan Copper Limited (HCL) is the sole producer of Cu in India is able to meet about
42% of country’s requirements, i.e. about 23,000 tons in 1977-78.
Gold (Au): India’s gold reserves are estimated to be 3.15 million tons (1977); a majority of
them located in Karnataka. The gold content of these reserves ranges from 5.65 to 19.98
gm/ton of ore. Minor deposits of gold have also been found in the Hutti gold field
(Karnataka). The entire production of gold in India is by the govt. of India’s Bharat Gold
Mines Limited (BGML) & the Karnataka state-owned Hutti Gold Mines Company. In 1977,
the Au production in India was 2854 kg compared with 3132 kg in 1976. This decrease can
be attributed to the shrinkage reserves, because of which, the gold production is unlikely to
go up in the future, unless, of course, new reserves are found.
Silver (Ag): India has no reserves of silver ores. However, small quantities of silver as a by-
product during the indigenous refining of gold, copper, and lead; the major part coming from
the lead smelters at Tundoo (Bihar) and the gold mines in Karnataka.
Lead (Pb) and Zinc (Zn): India has about 140 million tons of lead-zinc ores, of which
nearly 118 million tons are located in two areas in Rajasthan, namely, the Zawar mines and
the Rajapura-Dariba lead-zinc belt. The lead-zinc ores from Zawar mines are beneficiated at
the site to produce both zinc and lead concentrate. These concentrates are then processed; the
lead concentrate at Tundoo by the Hindustan Zinc Limited (HZL)’s smelter and the zinc
concentrate by another HZL smelter at Dabari. In 1977, HZL produced 46,500 tons of zinc
concentrate, which could meet about 36% of India’s total demand for 1977-78. In 1978, the
smelters at Tundoo and Visakhapatnam together produced 10,060 tons of lead.
Manganese (Mn): India is the 3rd largest producer of manganese in the world. The ore
deposits presently worked in India are located in Singhbhum, Panchmahals (Gujarat),
Balaghat (Madhya Pradesh), Bhandara and Nagpur (Maharashtra), Vishakhapatnam (Andhra
Pradesh), Sandur and Shimoga (Karnataka), Bonai, Keonjhar, and Koraput (Odisha), and
Banswara (Rajasthan). The total Mn reserves according to the Indian Bureau of Mines
(1977), are estimated to be 108 million tons. In 1977, the total production of Mn ore in India
was 1,774,000 tons.
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
Magnesium (Mg): India has extensive deposits of Mg in the form of magnesite (MgCO 3),
chiefly found in Chalk Hills of Salem district (Tamil Nadu). On the whole, India’s in situ
magnesite reserves are estimated to be 524 million tons, of which the existence of 33 million
tons has been conclusively established. Apart from Salem district, the other important
deposits are found in Idar (Maharashtra), Kurnool (Andhra Pradesh), Tiruchirapalli (Tamil
Nadu), Coorg (Karnataka), Dungarpur (Rajasthan), and Singhbhum. It should be nooted that
in some of these deposits, Mg is present as dolomite (CaCO3.MgCO3). Widespread reserves
of dolomite and magnesium limestones are found in Tamil Nadu, Andhra Pradesh, Bihar,
Madhya Pradesh, Rajasthan, and Odisha.
Molybdenum (Mo): Exploration surveys in Andhra Pradesh and Tamil Nadu have shown
that primery molybdenite (MoS2) occursin the quartz veins that traverse porphyritic granites
and, at places, in the granite itself. Mo in a base metal sulphide that is association with Cu
ores is found at Rekha and Bhatin in the Singhbhum district. Preliminary beneficiation of the
Mo ores has indicated the recovery during concentration to be 95%.
Tin (Sn): Tin is not extracted commercial scale in India although tin deposits have been
detected in Ranchi and Haziribagh (Bihar). The entire present requirement of almost 10,000
tons per year is being met by imports.
Titanium (Ti): Abundant quantities of ilimenite (FeO.TiO2) are found in the beach sands
along a 160 km stretch of the Kerala coast. In fact, a particular 23 km coastal strip contains
35 million tons of ilimenite and 3 million tons of rutile (TiO 2). The ilimenite from Kerela
contains a high % (55 %) of titanium. Smaller deposits of ilimenite occur near Tuticorin
(Tamil Nadu), Waltair (Andhra Pradesh), and Ganjam district (Odisha). The total reserves of
ilimenite in the form of beach sands are estimated to be 133 million tons. Apart from the
beach sand deposits, small quantities of massive and crystalline ilimenite are found in
Bhagalpur district (Bihar) and Kisengarh and Jodhpur (Rajasthan). The beach sands of Kerala
contain a mixture of minerals sands whose specific gravities vary from 2.3 (silica) to 4.9
(monazite).
Tungsten (W): The presence of tungsten minerals has been detected in certain parts of the
country, namely, Chandapathan in Bankura district (West Bengal), Agargaon in Nagpur
district (Maharashtra), and Degana (Rajasthan); the present production of tungsten comes
from the first two sources. The volume of tungsten concentrate produced in 1977 was 43,046
kg, of which Rajasthan accounted for 90% and West Bengal for 10%.
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Chapter 1 Introduction to Non-Ferrous Metal Extraction
Vanadium (V): India depends entirely on imports to meet its vanadium requirements
although vanadium-bearing titaniferrous magnetite (Feo.Fe2O3) has been located near
Dublabera in Singhbhum district and in Mayurbhanj district (Odisha). Also, a small deposit
near Nausahi in Keonjhar district (Odisha) is also known to contain vanadiferrous iron ores.
The total volume of vanadiferrous magnetite ores in India is estimated to be approximately 26
million tons.
16
CHAPTER-2
Atomic Number: 29
17
Chapter 2 Extraction of Non-Ferrous Metals
Then go for froth floatation, where addition of CaO as P H controls and Xanthate as collecter,
where we separate Cu sulphide from a mixture of Cu Sulphide, Lead Sulphide and Zinc
Sulphide. The Cu Sulphide contains 15-35% Cu, 15-35% Fe, 25-35% S, 3-15% gangue.
18
Chapter 2 Extraction of Non-Ferrous Metals
In conventional plant, roasting carried out in multiple hearth roaster with gradually
downward movement of feed having gradual increase in temperature of each hearth by fuel
firing as 5500 C. Where as in newer route, roasting carried out in fluidized bed roaster at
about 5500C. The product is SO2 gas which finally used for manufacturing for H2SO4.
The principal reactions takes place in roasted calcine contains Cu Sulphide and Fe
oxides of Fe and mixed sulphates of Fe and Cu given as
Reaction 2.1:
Reaction 2.2:
Reaction 2.3:
Reaction 2.4:
Reaction 2.5:
Reaction 2.6:
Reaction 2.7:
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Chapter 2 Extraction of Non-Ferrous Metals
Smelting:
It seeks to separate the metal sulphides in an ore concentrate or calcine from the
gangue by charging the furnace with suitable charge along with flux at about 12500C. During
smelting two separate layers are formed, as slag and matte layer having specific gravity 2.8-
3.8 gm/cm3 and 5.0-5.5 gm/cm3 respectively. If gangue and iron oxides present in the
concentrate/calcine to be smelted combine during smelting to form iron silicate slag. If iron
oxide insufficient the lime add as flux to form an iron calcium silicate slag. The melting point
of slag approximately 11500C and for fluid slag with a low Cu content, the temperature at
about 12500C.
Exchange reaction takes place between oxides and sulphides of Cu and FeS present in
furnace charge.
Reaction 2.8:
Reaction 2.9:
Reaction 2.10:
20
Chapter 2 Extraction of Non-Ferrous Metals
These reactions occur because O2 has a greater affinity for Fe than Cu in Ellingham
diagram. The unoxidised iron sulphide reduces the higher oxides of iron to ferrous oxide as
Reaction 2.11:
Reaction 2.12:
Smelting determine the extent of oxidation of FeS in charge to slag object is to
produce a matte contains 35-45% Cu, 20-22% S, 25-35% Fe. Smelting not only minimize the
loss of Cu to slag, but also provides a matte with a sufficient quantity of iron sulphide for use
in the next stage as converting.
Smelting conventional route occur in reverberatory furnace and electric furnace,
where in newer route flash smelting and continuous smelting takes place. The conventional
route, electric furnace because a large volume of combustion gas generation avoided and
facilities both recovery of so 2 and cleaning of furnace gases.
Converting: The purpose of converting is to remove Fe, S, and other impurities from matte.
Generally side blown converter used.
The capacity of converter is 100-200 tons, 4m diameter and 9 m in length. Lined with
a layer of Chrome-magnesite refractory about 40 cm thick. Oxidizing atmosphere inside the
converter by supply of O2 enriched air through the tuyere of 5 c.m. with 40 in number. The
total volume of gas is 600 m3/min. The product is blister Cu and slag. So, the Cu converting
namely slaging stage and blister formation stage.
(i) Slaging Stage: The iron sulphide present in matte is oxidized and oxide is slaged
out by addition of siliceous flux. The reactions are
Reaction 2.13:
Reaction 2.14:
Mainly three process are done as
Adding freshly obtain matte.
Blowing of air.
Slag gets skimmed off by tilting.
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Chapter 2 Extraction of Non-Ferrous Metals
The slag contains 2-9% Cu, 40-50% Fe, 20-30% SiO2, and 1-5% (CaO+MgO).
Conventionally, Cu is recovered from the slag produce in converter by transferring the slag in
molten state to a smelting furnace, where in case of newer process, metallic values of the slag
recovered by employing either an electric furnace with provision for cleaning the slag or by
slow cooling of slag followed by grinding and floatation.
(ii) Blister Formation Stage: After slagging converter contains Cu2S known as white
metal because of its appearance. In blister Cu formation stage, Cu2S is oxidized to form Cu
by combination of reaction.
Reaction 2.15:
Reaction 2.16:
Reaction (Overall) 2.17:
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Chapter 2 Extraction of Non-Ferrous Metals
When white metal (Cu2S) is oxidized the S content in bath decrease about 19.5% and
hence, the bath split into two layers as
Top sulphide layer of less dense.
Bottom Cu layer of more dense contain about 1.2% S.
As oxidation continues the sulphide layer (liquid b) decrease and Cu layer (liquid c)
increase. The relative volume of two phases determined by Lever rule.
The blister Cu contents 0.02-0.05% S along with 0.2-0.5% dissolved O2.
Refining:
The purpose of refining to get Cu extraction is twofold as
First, to obtain metal in pure form.
Second, to recover precious metals containing in blister Cu produced.
(i) Fire Refining: The purpose is to remove S from liquid blister Cu as SO2 by
oxidation with air and eliminates O2 by introducing hydrocarbons. In this case, the refining is
done in reverberatory furnace of 400 ton of capacity contains blister Cu get oxidized to
recover Cu removing the impurities such as S, Fe, Se, Zn by converting its corresponding
oxides and then skimmed off. But, some Cu also in the form of oxides.
To prevent Cu loss poling with green branches used to reduce Cu 2O using
hydrocarbon or some other reducing gases. In this case, the purity of Cu obtained 99.97%.
Fire refining is also done in rotary type refining furnace, where blister Cu directly treated by
blowing air.
(ii) Electrolytic Refining: The purpose is to further refined the fire-refined Cu by
electrolysis. The electrolysis done in a electrolytic refining tank made of concrete or wood of
3-5 m deep and utilization minimum space with maximum cathode and anode area. The
electrolyte is CuSO4, H2SO4, some glue and alcohol at temperature 50-600 C.
Cu transferred from crude anode to pure cathode. Impurities in blister Cu such as Fe,
Co, Ni, Se, Te etc. go into the solution and precious metals get collected below anode known
as anode slime.
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Chapter 2 Extraction of Non-Ferrous Metals
Process: Enriched preheated air or pure O2 used to increase combustion rate and
autogeneous smelting. The gases coming out rich of SO 2 due to high combustion rate and
used for H2SO4 manufacturing.
Process is autogeneous provide exothermic heat. Air used as oxidant to preheated.
The composition of concentrate used in flash smelting has Chalcopyrite (CuFeS 2) 66%,
Pyrite (FeS2) 24%, gangue (SiO2) 10%. Whereas the Cu matte contains 70% Cu, 8% Fe, 22%
S, slag contains Fe 40% at furnace temperature 13000 C.
Main reactions of flash smelting of Cu concentrate are mentioned below
Reaction 2.18:
Reaction 2.19:
Reaction 2.20:
Reaction 2.21:
Reaction 2.22:
Reaction 2.23:
Reaction 2.24:
Reaction 2.25:
24
Chapter 2 Extraction of Non-Ferrous Metals
Continuous Smelting:
It encompass smelting and converting in a single vessel i.e. Cu concentrate charged at
one end and Cu metal withdrawn continuously at the other end.
Mainly three are three processes, given below
(a) WORCRA. (b) Noranda. (c) Mitsubishi.
(a) WORCRA Process:
This name divided as the first 3 alphabets stands for the developers and last 3
alphabets for the place.
Features:
Counter current movement of gas and concentrate. So, continuous production
of blister Cu.
Directly blister Cu i.e. metal instead of matte form.
Combine smelting and converting.
The heat required for reaction directly obtained as the reaction is exothermic.
Counter movement cause continuous production of H 2SO4 due to continuous
extraction of gas.
Cu% continuously obtains from slag by means of cleaning operation.
Process:
The process combines 3 different operations in a single furnace as
Continuously smelting
Continuously converting
Continuously slag cleaning by conditioning and settling
Efficiency:
It increases by means of counter current movement increase the reaction surface area
in the smelting and converting zone. Hence, effective removal of impurity occur i.e. mainly
Fe due to counter movement of slag and matte. As a result, Cu gets reverted back to matte
and obtain.
Advantage:
Continuous process
Capital cost low
Concentrate passes large surface area. Hence accelerate the reaction.
25
Chapter 2 Extraction of Non-Ferrous Metals
Disadvantage:
Not durable
Operating cost is high
26
Chapter 2 Extraction of Non-Ferrous Metals
27
Chapter 2 Extraction of Non-Ferrous Metals
28
Chapter 2 Extraction of Non-Ferrous Metals
This refining technique applied only for ultra pure material i.e. low concentration of
impurity. If ‘A’ is solvent and ‘B’ is solute then addition of A with B caused increase in
melting point of B as due to bond formation as A-A, A-B, B-B.
When A at composition of ‘P’, it get melted and when it is at ‘Q’ get solidify, whereas
the same compositions for B at equilibrium condition is less than A.
The free energy difference is
( ) () ( )
Atomic Number: 30
Willemite Zn2SiO4
29
Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.26:
Reaction 2.27:
Reaction 2.28:
30
Chapter 2 Extraction of Non-Ferrous Metals
In most cases, fluid bed roaster allotted instead of hearth roaster because of following
advantages
Autogeneous
Good control over high through put of Zn calcine
Generate SO2 suitable for acid production
31
Chapter 2 Extraction of Non-Ferrous Metals
4. Electrolytic Reduction:
In this case, when Zn immersed in their salt solutions, rapidly establish a reversible
potential. Since the activation over potential is low, the displacement behavior exhibits a
good correlation with the electrochemical series of standard potentials.
5. Imperial Smelting Process (ISP):
The process inside the furnace based on reaction i. e. reduction of ZnO by C in the imperial
blast furnace gives rise to Zn in vapour form which gets condensed by using molten lead.
32
Chapter 2 Extraction of Non-Ferrous Metals
ISP furnace is of square cross section consists of water jacket brick lined shaft.
Feed is given from the top of the furnace at positive pressure where we
introduced preheated coke and sinter through a double bell charging system.
ISP consists of two condensers.
Reaction 2.30:
Reaction 2.31:
Reaction 2.32:
Reaction 2.33:
33
Chapter 2 Extraction of Non-Ferrous Metals
Carbon does not reduce ZnO until 11200 C, since at this temperature Zn gets
vaporized. After reduction complete the molten slag and Pb are taken out from the furnace
hearth at the melting point of the slag. Hence, Zn gets collected. So the reaction (2.31) may
backward as due to the difference.
Lead Bullion (Rich 70-80% Pb):
It is the mixture of Pb and precious metal, where preheated coke 800 0 C and sinter
21% Pb are charged from the top of ISP furnace. So at bottom collect precious metals such as
Au, Cu etc. and this liquid is known as Lead Bullion.
Advantages of ISP:
Economical production of Zn.
Efficiency overall high but Zn recovery expensive.
Entire amount of Au, Sb etc. recover.
Capacity large.
Complete mixed charge of Zn and Pb simultaneously charged and
recovered.
Operational cost is low.
No additional C required.
34
Chapter 2 Extraction of Non-Ferrous Metals
In bath,
Reaction 2.34:
Reaction 2.35:
Above bath,
Reaction 2.36:
Reaction 2.37:
35
Chapter 2 Extraction of Non-Ferrous Metals
The excess heat gets collected by boiler located in gas collection system and the
control of coal to air ratio determine the extent of heat released and maintained the bath
temperature at about 12000 C.
First, the elimination of Zn is slow but reaching 1000 0 C get accelerate so Zn% 2.5%.
Whereas Zn 1% in slag product contain 93-94% Zn. Fume leaves furnace at 11000 C by
combustion which effected by water cooling tower at 2000 C.
Then fume enters to big house where Zn collected and dispatched to Zn smelter on an
electrolytic plant.
36
Chapter 2 Extraction of Non-Ferrous Metals
Anglesite PbSO4
37
Chapter 2 Extraction of Non-Ferrous Metals
Hence, free Pb gravitated to the wall of furnace, and was trapped out at working
temperature 10000 C. Thick crust allow to accumulate slowly down even stopped reaction by
the action of the air blast.
38
Chapter 2 Extraction of Non-Ferrous Metals
Bosh: Purpose is to retard the descent of charge in front of tuyere as material melts
away.
Newer Blast Furnace Reduction: Furnace area increases from the throat to downward at the
end of tuyere in this case following advantages are occur
PbO also helps in reducing PbS left unroasted in the sinter machine and hence,
combine with Silica (SiO2) in charge to form 2FeO.SiO2. Hence, lower the melting point of
slag and increase the fluidity of metal layer.
Reaction 2.39:
Finally helps to reducing the Pb as
Reaction 2.40:
Disadvantage of Newer Process:
A thick mushy layer form in between matte and slag which interfering into the
separation
A wide variation in temperature as 2000 C at top to 12000 C at tuyere
In blast furnace reduction produce 4 distinct layers on the basis of their specific
gravity as
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Chapter 2 Extraction of Non-Ferrous Metals
OR
Mainly Speiss closely relate in the presence of As and Fe in the blast furnace.
Reaction 2.41:
Speiss have high content of Cu which get recovered by treated it in converter to get
Cu in blister form. Finally, the Pb bullion or base bullion get from the blast furnace which on
refining produce pure lead.
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Chapter 2 Extraction of Non-Ferrous Metals
As Zn layer (first layer) has higher melting point. So, solidify first.
41
Chapter 2 Extraction of Non-Ferrous Metals
Dezincing:
42
Chapter 2 Extraction of Non-Ferrous Metals
43
Chapter 2 Extraction of Non-Ferrous Metals
Pentalandite – [(NiFe)9S8]
Violarate – [Ni2FeS4]
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Chapter 2 Extraction of Non-Ferrous Metals
45
Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.42: → ( )
Reaction 2.43: ( ) →
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Chapter 2 Extraction of Non-Ferrous Metals
The Ni oxide reduce by coke in fuel fired furnace or electric furnace, and then cast
into Ni metal anode. These anodes are electrolytically refined in a bath contains 60 gm/lit
Ni+2, 95 gm/lit SO42-, 35 gm/lit Na+, 55 gm/lit Cl-, 16 gm/lit H3BO3. This electrolysis carried
out at 600 C. Cu remove by cementation with active Ni powder, Fe and other impurities
remove by aeration of electrolyte, Co remove by Cobaltic Hydroxide for further Chlorine
oxidation. Electrolyzed Ni analyzes about 99.93% Ni.
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
Asbestos – CaSiO3.2MgSiO3
Kainite – MgSO4.KCl.3H2O
Reaction 2.45:
Reaction 2.46:
Again in Pidgeon process MgO reacts with Ferro-Si to give Mg vapour in vacuum as
Reaction 2.47:
Dow Process:
It is used for production of Mg from sea water containing MgCl2. Sea water used
because of
Economically Mg extract.
Uniformity of Mg content.
The sea water contains MgCl2.1.25 H2O as feed material. In this process, the
following reactions occur as given below
Reaction 2.48:
Reaction 2.49: ( )
Reaction 2.50: ( ) ( )
Reaction 2.51: ( ) ( )
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Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.52:
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Chapter 2 Extraction of Non-Ferrous Metals
Electrolysis of MgCl2:
Mg is reactive metal has high decomposition potential. Therefore, aqueous
electrolysis H2 evolution occurs before decomposition of MgCl2. In electrolysis, MgCl2 get
fluidized by use of flux and to increase the density of bath so that metal liberated at cathode
floats on the surface of electrolyte and not sink.
The electrolytic cells are two types lined and unlined. First one provides separate
cathodes made of steel where the later one is steel wall of itself used as cathode. In both
cases, graphite used as anode which is inert i. e. not consumed to the metal divert away from
anode zone and Chlorine gas collect in a hood and metal to a pool. Chlorine gas from the
anode used to dry incoming MgCl2 and chlorinated Mg (OH) 2.
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Chapter 2 Extraction of Non-Ferrous Metals
The product Mg is gaseous form removed from the retort to avoid possibility of back
reaction during cooling and condensation.
The reaction occurs in two ways at 12000 C
Absence of lime
Reaction 2.54:
Presence of lime
Reaction 2.55:
The process is highly endothermic reaction, so large heat input required. There is
small addition of CaF2 or MgF2 added to speed of the evolution of Mg vapour. Since, vapour
pressure of Mg is not altered the effect of fluoride addition is considered catalytic.
Equipment and Operation:
The retort is of 25 cm dia. and 3m length inserted horizontally in the furnace made of
Nichrome steel with 15% Ni, 28% Cr, 1.25% Mn, 1.5% Si, 0.3% C and Fe balanced in air
cooled continuously batch process. The furnace heated either by gas or by electricity.
The charge is of 1:6 ratio of Fe-Si to calcine dolomite of 100 kg weight. Heating
carried out to vaporize structurally combined water. The temperature raised about 1150 0 C
and in vacuum. At this stage, Mg vaporizes and condensed by baffles. Application of vacuum
stopped and seal broken condensed Mg removed out. Approximately, 120 ton dolomite with
12 tons Ferro silicon gives rise to 10 tons of Mg.
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
Then the liquor cooled little below 1000 C and completely pressurized is to settling
and clarification section red mud get deposited in presence of starch which speed of the
settling. Any remaining red mud gets separated by a series of washers by encountering flow
of hot water. After washing the solution the remaining residue consists of ferric hydroxide,
silica and alumina.
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Chapter 2 Extraction of Non-Ferrous Metals
Hot liquor tapped by heat exchanges to obtain cool liquor. Then cool liquor under
precipitation carried out a temperature below critical point. Then Al(OH) 3 used for separation
precipitate from liquor in a series of thickeners. The product, a coarse hydroxide is finally
calcined in a rotary kiln to produce a anhydrous Al2O3.
Reaction 2.61: ( ) ( ) ( )
Cryolite bath get enhanced conductivity by addition of CaF2 and NaF. At 10000 C
density of molten cryolite is 2.1 gm/cm3 and Al2O3 is 3.96 gm/cm3. Al liberated heavier than
bath and sinks at bottom. Higher the amount of Al2O3 in bath, the higher its density and
consequently the sinking of Al is rendered more difficult.
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.64:
Reaction 2.65:
The cell consists of rectangular refractory lining steel box with l=5 m, w=2 m,
depth=1 m. Cathode lining consists of refractory bricks faced with C mixed tar binder. A
consumable graphite electrode serves as anode. A Fe plate and Fe bar form the cathode are
embedded in the C mixture. A tap hole is there, through which metal get collected at the
bottom of the hole.
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Chapter 2 Extraction of Non-Ferrous Metals
C gets backed in steel mould to produce anode. Fe pins are inserted by electric
contact. The baked C electrodes and cathode lining must be sufficiently strong and dense.
Cell Operation:
During operation, the cell bath is filled with cryolite and anode lowered into it. A
current is passed through it until cryolite melts (M. Pt. – 9900 C).
When bath attains a molten state addition of alumina commenced. The alumina
decomposes to yield Al and O2. The necessary heat being supplied by the resistance offered
by both the electrodes and the electrolytes.
2.6.3.4 Anode Effect:
If alumina content of bath (normally 5-10%) falls below 2% then normal contact
between the anode and bath is interrupted by the gas film in which abruptly increases positive
resistance. As a consequence the normal operation ceases. This effect is called anode effect.
Under certain conditions, the electrolytes of fused salt is associated with the periodically
occurring phenomena in which the terminal voltage increases to high value and current
density decreases to a lower value from their normal value. This effect is known as anode
effect.
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Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.67: ̅
Anodic Reaction:
Reaction 2.68: [ ] ̅
Reaction 2.69: [ ] ̅
Reaction 2.72:
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Chapter 2 Extraction of Non-Ferrous Metals
Hoope’s Process:
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
ALCAN Process:
Bauxite reduced to Al alloy.
Reduction carried out in EAF at 2000 C presence of coke.
The alloy is reacts with preheated AlCl3 vapour in reactor.
Reaction 2.76: →
Reaction 2.77: →
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
As mainly Zr constitute with HF. So our first aim is to separate HF from Zr.
2.7.3.1 Pyrometallurgical Methods:
a. Differential Oxidation of Tetrachloride reaction
Reaction 2.78:
Reaction 2.79:
b. Formation of Lower Chloride of Zr reaction as
Reaction 2.80:
c. Differential reaction of double chlorides with alkali chloride. The reactions are
Reaction 2.81:
Reaction 2.82:
2.7.3.2 Reduction of Zr Compound to Metal:
Metallic Zr conventionally produced by metallothermic reduction of Zr tetrachloride.
Kroll’s process of Mg reduction is most popular method. Recently Zr successfully produced
by the fused salt electrolytes of double salts such as Cs2ZrCl6 dissolved in alkali chlorides.
2.7.3.3 Production of Mill Products from Sponge Metal:
Conventional induction melting Zr alloys in graphite crucibles in unsuitable due to the
prohibitive C pick up. At present, consumable electrode is melting with water cooled Cu
moulds employed for tonnage melting of alloys. Procedure evolved for
Compaction of sponge briquettes with alloying additions
Fabrication of consumable electrode
Controlled vacuum arc melting
For homogenizing the alloy composition and for removing the volatile impurities,
double vacuum arc melting is used. The shaping of alloy and extrusion of tubes are achieved
through a series of steps, each of which need special precautions.
2.7.4 Uses of Zr:
Non nuclear applications: Flash bulbs in the form of thin foils and ceramics as
an oxide.
Nuclear reactor used as cladding element.
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Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.83: →
The reaction is carried out in a stainless steel container for externally heating by gas
or electricity. Exothermic reaction occurs. After reaction is over the Ti sponge is recover
either by dissolving MgCl2 and excess Mg by leaching with cold dilute hydrochloric acid or
by distilling off MgCl2 and excess Mg by vacuum heating. The residue is pure Ti sponge. The
maximum yield is 96% because of
Efficient Scavenger w.r.t impurity chlorides such as FeCl3 and AlCl3.
Better conductivity of NaCl compares to MgCl2 and hence, reaction is
exothermic.
NaCl-MgCl2 leads a better separation of metal from slag.
2.8.3.2 Hunter Process:
The reduction of TiCl4 by Na is to give Ti known as Hunter process and written as
Reaction 2.84:
The reaction is highly exothermic, there is a series of reactions occur as
Reaction 2.85:
Reaction 2.86:
Reaction 2.87:
Reaction 2.88:
Reaction 2.89:
Reaction 2.90:
Reaction 2.91:
Reaction 2.92:
Reaction 2.93:
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Chapter 2 Extraction of Non-Ferrous Metals
The anode reaction takes place at a metal surface where sodium metal, fused NaCl,
Cl- ions are available for salvation of Na+ ions. The Cathodic reaction takes place at a metal
site where soluble Ti in fused salt is available and Cl- ions released completely in the anodic
reaction.
2.8.4 Uses of Ti:
The sponge Ti produces in Kroll’s process and ductile Ti produce in Hunter process.
Main uses of Ti overally is
Jet engine components
Air frames
Missiles and space craft
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Chapter 2 Extraction of Non-Ferrous Metals
Reaction 2.97: ( )
69
Chapter 2 Extraction of Non-Ferrous Metals
Pulverize coal separate and precipitate out AlCl3. Deleading of Sn by SnCl2 based on
Reaction 2.99:
A Sn-Pb alloy removes from PbCl2-SnCl2 mixture by melting in contact with Zn.
Reaction 2.100:
Any excess Ca or Mg is removed by adding NH4Cl according to the reaction
Reaction 2.101: ( ) ( )
70
Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
72
Chapter 2 Extraction of Non-Ferrous Metals
73
Chapter 2 Extraction of Non-Ferrous Metals
74
Chapter 2 Extraction of Non-Ferrous Metals
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Chapter 2 Extraction of Non-Ferrous Metals
76