Bansal Classes Metallurgy

MATALLURGY
M ATA L L U R G Y
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MATALLURGY
ORES, MINERALS AND EXTRACTIVE METALLURGY Ores and minerals Extractive metallurgy Commonly occurring ores of iron, copper, lead, magnesium and aluminium. (Mains Only : Tin and silver) (Chemical principles and reactions only; industrial details excluded): Carbon reduction method (iron)(Mains Only : Tin also), Self reduction method (copper and lead), Electrolytic reduction method (magnesium and aluminium), (Mains Only : cyanide process :Gold and silver)
ORES AND MINERALS Metals occur in nature in combined form as minerals. Minerals from which a metal can be profitably extracted is termed as ore. e.g. FeS2 is a mineral of iron, not anore. IMPORTANT ORES OF SOME METALS (Principal ore is given in bold letters) Iron: In the combined state, iron occurs in the following minerals. Haematite, Fe2O3 Magnetite, Fe3O4 Limonite, 3Fe2O3 3H2O Spathic iron ore, FeCO3 Tin: Cassiterite or tin stone, SnO2.
Copper occurs in the native state as well as in the compounds form. The natural ores of copper are Malachite, Cu(OH)2 CuCO3(green) Copper pyrites, CuFeS2 Azurite, Cu(OH)22CuCO3 Cuprite or ruby copper, Cu2O Copper glance, Cu2S Cu5FeS4(peacock ore) Lead: Galena, PbS Anglesite, PbSO4 Stolzite, PbWO4 Magnesium : Dolomite, MgCO3 CaCO3 Magnesite, MgCO3 Kiesserite, MgSO4H2O Schonite, MgSO4K2SO46H2O Cerussite, PbCO3 Wulfenite, PbMnO4
Carnallite, MgCl2KCl6H2O Epsomite(epsom salt), MgCO37H2O Kainite, MgSO4KCl3H2O
Magnesium is widely distributed in nature in rocks, spring and seawater. In rocks and silicates it occurs in mineral like olivine (Mg2SiO4), spinel (MgAl2O4), talc (Mg3H2(SiO3)4), asbestos (CaMg3(SiO3)4), etc. Aluminium: Aluminium is the third most abundant element of earths crust. Oxides: Corundum, Al2O3; diaspore, Al2O3H2O and bauxite, Al2O32H2O. Fluorides: Cryolite, Na3AlF6 Silicates: Feldspar, KAlSiO3O8, mica(KAlSi3O10(OH)2) and kaolinite (Al(OH)4, Si2O5) Basic Sulphates: Alunite or alumstone, K2SO4Al2(SO4)32Al(OH)3 Basic Phosphates: Turquoise, AlPO4Al(OH)3H2O Aluminates: Aluminates of Mg, Fe and Mn. Silver in the native form is associated with copper and gold. The main ores of silver are Argentite or silver glance, Ag2S Horn silver, AgCl Proustite, 3Ag2S As2S3 Pyragyrite, 3Ag2S Sb2S3
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MATALLURGY
(a)
(b)
(c) (d)
TYPES OF METALLURGY pyro metallurgy : Extraction of metal from ore by using heat energy. Seteps involved are : Calcination, roasting, reduction etc. Ex. Less reactive metals : Cu, Fe, CO, Ni, Zn, Snm Pb etc. Hydro metallurgy : (Ag, Au, Cu) - This is wet metallurgy process Cu Pyro + Hydro Ag and Au By cynide process. Steps are : (i) Complex formation (ii) Metal displacement NaCN (i) AgCl or AuCl Na[Ag(CN)2] (Sodium argento cynide) Zn (ii) 2 Na [Ag(CN)2] Ag + Na2 [Zn(CN)4] (Impure) Electrocal metallurgy : This process used for highly electro positive metal (s-block and A ) metal obtained by electrolysis of fused salt/anhydrous medium. Ion exchange metallurgy : Transuranic element are obtained by this method. STEPS INVOLVED IN THE EXTRACTION OF METALS The extraction of metal from its ore is completed in the following four steps. (a) Crushing and grinding (b) Pulverisation (c) Concentration of the ore (d) Reduction to the metal (e) Refining of the metal. CONCENTRATION OF THE ORE The removal of impurities from the ore is called its concentration. It is carried out in one or more of the following steps. Thes undesired impurity are gengue or matrix.
By Physicals seperation (a) Gravity separation (Lavigation) : The method of concentration of the ore is based on the difference in the specific lavigation gravities of the ore and the gangue particles. Powdered ore is agitated with a running stream of water. The lighter gangue particles are taken away by water while heavier ore particles settle down. Ex. Oxygenated ores. (b) Froth Floatation Method : This method is mainly employed for the concentration of sulphide ores. The method is based on the difference wetting characteristics of the gangue and the sulplide ore with water and oil. The gangue preferrentially watted by water and the ore by oil. The crushed ore along with water is taken in a floatation cell. Various substances are added depending on the nature of the ore and a current of air is blown in. The substances added are usually of three types. (i) Frothers : The generate a stable froth which rises to the top of the tank. Example of frother is pine oil, Eucalyptus oil etc. (ii) Collectors or floating agents: These attach themselves by polar ground to the grain of the ores which then become water repellant and pass on into the froth. Example : sodiumethyl / ethyly xanthate. (iii) Activators or Depressants : These reagents activate or depress the flotation properly and help in the separation of different sulphide ores present in a mixture. An example of depressant is NaCN, An activator is CuSO4. (c) Magnetic Separation: If the ore and not the gangue or the gangue and not the ore is attracted by a magnet, the two can be separated by this method.
FROTH SKIMMER
COMPRESSED AIR
CONCENTRATED ORE GANGUE
FROTH FLOATATION
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OIL WATER MIXTURE
Fig.2
MATALLURGY
Magnetite (Fe3O4) is concentrated by this method, (FeWO4) wolframite removed from SnO2, FeO removed from chromite (Cr2O3FeO). By Chemical Separation: Some of the ores are concentrated by means of chemical treatment.
ORE
NONMAGNETIC PARTICLES
(i)
Leaching: It involues the treatment of the ore with a suitable reagent. as to makee it soluble while impurity remain insoluble. The ore is recoverd from the solution by suitable chemical method. Beyers Process : Ex. Bauxite ore contain impurity Fe2O3, TiO2, SiO2 when it dissolve in aq. NaOH/pressure + 150C bauxite is dissolve but other are not dissolve. 2 NaAlO2 + H2O Al2O3 + 2 NaOH Al(OH)3 + NaOH NaAlO2 + 2H2O
| | Al2O3 + 3H2O Cyanide process: Their process used for Au, Ag by (Mac-Arthur forrest cyanide process).
Fig.1 MAGNETIC SEPARATION
(ii)
CALCINATION Calcination is a process in which ore is heated, generally in the absence of air, to expel water from a hydrated oxide or carbon dioxide from a carbonate at temperature below their melting points. For Example : (i) Al2O3. 2H2O (ii) 2Fe2O3. 3H2O (iii) CaCO3 (iv) CaCO3. MgCO3 (v) MgCO3 (vi) ZnCO3 (vii) FeCO3 Al2O3 + 2H2O, 2 Al(OH)3 Al2O3 + 3 H2O 2Fe2O3 + 3H2O CaO + CO2 CaO + MgO + 2CO2
MgO + CO2 ZnO + CO2 FeO + CO2
Advantanges of Calcination: (i) Moisture is removed. (ii) Organic matter is destroyed (iii) The hydroxide and carbonates ores are convered into their oxides. (iv) The metal become porous and easily workable. ROASTING (Metal sulphides Metal oxide + SO2) The removal of excess sulphur contained in sulphide ores by heating in an excess of air is called roasting. The cencentrated sulphide ore is heated in reverberatory furnace, below its melting poing of fusion temperature in the presence of an excess of air with or without the addition of an external substance. In roasting desinite chemical like oxidation, chlorination etc., take place but in calcination does not
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MAGNETIC PARTICLES
ELECTROMAGNETIC WHEEL
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MATALLURGY
occur any major chemical changes. (i) 2 ZnS + 3O2 2 ZnO + 2SO2 (ii) ZnS + 2O2 ZnSO4 (iii) 2 Cu4s + 3O2 2 Cu2O + SO2 (iv) 4 FeS2 + 11O2 2Fe2O3 + 8SO2 (v) HgS + O2 HgO + SO2 (vi) 2 As2S3 + 9O2 2 As2O3 + 6 SO2 Advantages of Roasting: (i) Excess of sulphur is removed as volattile oxide. S + O2 SO2 (air) (ii) The metal sulphide is converted into metal oxide. (iii) Impurities of arsenic and antinony are removed as their volatile oxides. Sb4 + 3O 2 2Sb2O3 As4 + 3O 2 2As2O3 Types of Roasting : (a) oxidising S SO2
SO2
S
SO2 4
(b) Partical oxidising or sulphating
(c) Chlorinating In partical roasting process : In Pbs or ZnS 2PbS + 3 O2 2PbO + 2 So2 PbS + 2 O2 PbSO4
S Cl
By substitution reaction
(a)
REDUCTION OF ORE OF THE METAL The calcined roasted ore in then reduced to the metallic state in either of the following ways. Reduction by carbon (Smelting) : (This is common method of reduction) Reduction of the oxide with carbon at high temperature is known as smalting. The oxides of less electropositive metals like Pb, Zn, Fem Sn,Cu, etc,are reduced by strongly heating them with coal or cock, in the blast furnace. Slag : Fusible metarial during reduction process. Slag : Gangue + substance (for remove gangue). Fluxes acidic : Borax, SiO2 (Remove basic impurity) Fluxes basic : MgO, MgCO3,CaCO3 (Remove acidic impurity) (RA Reducing agent)
Smelting: * Concentrate ore (ore + gangue) + RA (carbon) + Flux
Metal + Slag + gases * Cr2O3 Carbon is not used for reduction Mn3O4 Carbon is not used for reduction MnO2 Carbon is not used for reduction * Coke is not used for reduction of s-block oxide Al2O3 (due to formation of metalcarbides) CaO + 2 C CaC2 + CO Some reactions: (i) CuO + CO CO2+ Cu PbO + C Pb + CO Fe2O3 + 3C Fe + 3CO ZnO + C Zn + CO ZnO + CO Zn + CO2 (ii) (gangue) acidic impurity (flux) (slag)
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MATALLURGY
SiO2 + CaCO3 CaSiO3 + CO2 P2O5 + 3 CaO Ca3 (PO4)2 (iii) Basic impurity + Flux slag MgCO3 + SiO2 MgSiO3 + CO2 FeO + SiO2 FeSiO3 Note: Blue flame is obtained by burning of CO in smelting process. (b) Self Reduction: Compounds of certain metals are reduced to metal without using any additional reducing agent.ores of Cu, Pb, Hg etc. Their sulphide ores are partially roasted to give some oxide. This oxide is now reduced to the metal by the remaning sulphide ore at elevated temperatures in the absence of air. The process is known as self reduction. Self Reduction for Pb: Roasting 2 PbO + 2SO2 (i) 2PbS + 3O 2 (Galena) (Air) High temperature Absence of air 3Pb + 2SO2 PbS + 2PbO (unroasted ore) (roasted ore) (Self reduction) + Cu2S 6 Cu + SO2 (ii) 2 Cu2O (c) Metal Displacement method: In this method a water soluble compound is obtained from the ore. The aqueous solution of the compound is reacted with a more electropositive metal which displaces, the metal from the solution. (i) Zairvogel process for silver. 85 C Ag2S + 2O2 Ag2SO4 Argentite CuSO4 (aq) + 2 Ag (S) Ag2SO4 (aq) + Cu (Scrap copper) (ii) Seperation Ag by complex formation (Cynide process) Silver and gold are extracted by a method involving complex formation. Air Ag2S + 4 NaCN 2 Na [Ag(CN)2] + Na2SO4 (powdered argentite) 2 Na [Ag(CN)2] + Zn Na2 [Zn (CN)4] (aq) + 2 Ag Black ptt. (d) Electrolytic reduction This process is mainly used for the extraction of highly electropositive metals. Electrolysis is caried out in a large cells and a small amount of another suitable electrolyte is added which: (i) Lower the melting point of the main electrolyte (ii) Enhances its conductivity (iii) Reduces corrosion troubles Ex.: Na, K, Mg, Ca, Al, etc., e.g., Manufacture of metallic sodium (Downs process) Molten NaCl containing a little CaCl2 is electrolyzed between graphite anode and iron cathode. The various reactions that take place are
0
On Fusion :
NaCl
Na+ + Cl (Ions become mobile)
(e)
On Electrolysis : At Cathode : Na+ + e Na (reduction) (Metallic sodium) At Anode : 2 Cl Cl2 (g) + 2e Reduction by Al: This process is employed in the case of those metals which have very high melting points and are to be extracted fromtheir oxides. Cr2O3 + 2 Al 2Cr + Al2 O3 3 Mn3O4 + 8 Al 9 Mn + 4 Al2O3 REFINING OF METALS Metals obtained by the reduction of its compound still contains some objectionable substance and have to be refined.
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MATALLURGY
Depending upon the nature of the metal and impurties, the following methods are used for purification of the metals. (a) Liquation: This method is used for the refining of metals having low melting point and are associated with high metal uimpurities. Ex. Pb, Sn, Sb, Bi and Hg. The impure metal is heatd on the sloping hearth of a furnace. The pure metal flows down leaving behind the non-fusible material on the hearth. (b) Distillation : metals having low boiling point are refined by this method, for example, zinc, cadmium and mercury (c) Distribution method : The parkes process, is used for the disilverization lead (PbS + 01 to 1% Ag) is based on distrubution priciple. The principle follows as * Molten zinc and molten lean form a two phase system. * Silver is more siluble in molten zinc then the molten lead. * The Zn- Ag alloys is lighter than Pb and freezes fast. * The floating solidified Zn- Ag Alloy can be easily removed from molten Pb. * From Zn- Ag alloy, zinc is seperated by distillation. (d) Zone refining or fractional crystallisation: Metals of very high purity are obtained by zone refining. This refining method is based on the fact that impurities tend to remain dissolved in molten metal. Ge, Si and Ga used as semiconductors are refined in this manner. (e) Oxidation process (Pyrometallergical oxidation process) : These processes are used for refining of metals associated with impurities having high affinity for oxygen than the metal itself. Cupellation, pudding and bessemerization are important oxidation processes employed for refining different metals. (f) Electro-refinig of Metals : Metals such as Cu, Zn, Ag, Sn, Al, Ni, Cr are refining by this method. The impure metal is mede the anode of a electrolytic cell, while cathode is thin plate of pure metal. Electrolyte is the solution of a double salt of the metal. On passing the electric current pure metal from the anode dissolves and gets deposited at the cathode. The soluble impurities go into the solution while insoluble or less electropositive impurities settle down below the anode as anode mud or sludge . Ex. Electrorefining of copper Anode : Blister copper (90%) Cathode : Pure copper Electrolyte : An aqueous solution of CuSO4 (15% + 5 % dill H2SO4) Electrorefining of Pb (Betts Process) Anode : Impure lead., Cathode : Pure lead. Electrolyte : A mixture of PbSiF6 and H2SiF6 (g) (i) Vapour phase refining : Van-Arkel Process : Employed to get metal in very pure from of small quantities. In this method, the metal is converted into a volatile unsteadble compound. (e.g., ionide), and impurities are not affected during compound formation. The compound thus obtained is decomposed toget the pure metal. Employed for purification of metals like titanium and zirconium. 523 K Ti (s) + 2 I2 Ti l4(g) Impure 1700 K Ti(s) + 2I2(g) Til4(g) Monds process : Nickel is purified by using CO gas. This involves the formation of nickel tetracarbonyl. Ni(impure) + 4 CO [Ni(CO)4] Ni(pure) + 4CO Some other methods : Kroll collen process TiCl4 + 2Mg 2MgCl2 + Ti
(ii)
(h) (i)
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MATALLURGY
(ii) (iii)
IMI method TiCl4 + 4 Na 4 NaCl + Ti Amalgamation process for nobel metal Au, Ag from the native ore. distilled Almalgam (i) Hg(vapour) or powder + Hg
(ii) Metal
FURNACES. Furnaces are either powered by fuel (mostly coal, as in blast furnace or reverberatory furnace) or by electricity. Fuel fired furnaces generator maximum temperature of 1400-1500C while electric furnaces can supply as high as 3000 temperature. Kilns. When fuel and ore are mixed and heated. No reduction occurs. e.g. Lime Kilns. Blast Furnace.Fuel and ore are mixed and charged from the top of furnace and hot air is blown from the holes (tuyers) near the bottom. The ore is reduced as it descends down. Reverberatory Furnace.Material to be heated is placed on the hearth of a reverberatory furnace. As hot air is blown in (see fig.) flames rise and hit the concave top of the furnace, thereby turning in and heating the hearth. fuel and ore are separate in this case.
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AIR
Fig. 3
MATALLURGY
GENERAL CLASSIFICATION OF EXTRACTION PROCESSES An ore to be treated must first be examined. Following methods should be tried (in this sequence). Mechanical Separation If metal occurs in its native state(e.g. gold), it is simply separated mechanically by crushing the nuggets or rocks and separating it. Thermal Decomposition : If a particular compound can simply decompose on heating then the metal is recovered by simple heating. e.g. Hg from HgO. Two interesting processes are described below. (i) Monds Process. When nickel oxide is heated with water gas (CO + H2), H2 reduces nickel oxide to nickel, which readily combines with CO to form Ni(CO)4 , a highly inflammable, volatile gas. This gas, when separated out and heated to 180C, decomposes to give pure nickel. van Arkels Process. Many metals (e.g. zirconium) form volatile iodides which, when contacted with hot tungsten wire, release I2 and the metal is deposited on the wire. When sufficient quantity of metal has been deposited, tungsten core is bored out. This method is used for obtaining small quantities of highly pure metal. Displacement Method : In this method a cheaper metal, which occupies a higher place in electrochemical series, displaces a costlier metal from its salt solution. e.g. displacement of gold and silver from their solution by scrap zinc in cyanide process. Another example is treatment of lean ore of copper (containing very small amount of copper). Such ores are dug out and dumped in trenches in open. The rainwater collects in trenches and dissolves the sulphides when they are oxidised to sulphates by atmospheric oxygen. CuS + 2O2 CuSO4 (aq) After a year or two, dilute solution of copper sulphate is simply pumped out leaving behind all the mud and other impurities. This solution, when treated with scrap iron, precipitates copper. Cu2+ (aq) + Fe Fe2+ (aq) + Cu
(ii)
High Temperature Chemical Reduction. (i) By Carbon. e.g. in metallurgy of iron and tin (discussed later). (ii) Thermite Process : Reduction by aluminium is highly exothermic, so much so that the products are formed in molten state. This is thermite process. e.g. Cr2O3 + 2Al Al2O3 + 2Cr + heat (iii) Self Reduction as in the case od copper and lead (discussed later). ELECTROLYTIC REDUCTION (i) In aqueous solution and (ii) In fused melts, if the metal is too reactive. It is costly, hence it is resorted to only when no other method is available. e.g. for Na, Mg, Al etc. (discussed later).
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MATALLURGY
EXTRACTIVE METALLURGY IRON AND TIN Both iron and tin are extracted by the carbon reduction method . Extraction of Iron Iron is extracted from its principal ore, haematite. After the preliminary washing, concentration and roasting, the ore is smelted in the presence of coke and limestone in a blast furnace (fig.1). Roasted ore (8 parts) with desulphurized coke (4 parts) and limestone pieces (1 part) is fed into the blast furnace from the top. Preheated air is blown in through water-jacketed pipes called tuyeres fixed in the lower part of the furnace. There is a temperature gradient as we move from the bottom (temperature about 2000K) to the top (temperature about 500K) of the blast furnace. The blast furnace may be broadly divided into three main parts as described in the following.
CHARGE (ORE, LIMESTONE AND COKE)
WASTE GASES 4 4 4 K 4Fe4O4 4 CO 4Fe4O4 - CO4

SOLID CHARGE DESCENDS
CaCO4 CaO 4 CO4

GASES RISE
Fe4O4 4 CO 4FeO 4 CO4 4 4 4 4 K C4CO4 4CO FeO 4 CO Fe(S) 4 CO4 4 4 4 4 K e l t s I m p u r ei r o nm M o l t e ns l a gf o r m s 4 4 4 4 K

o s p h a t e s a n d S i l i c a t e s r e d u c e d , P h P a d p n S a s s i n t o m o l t e n i r o n
FIRE BRICKS
HOT AIR BLAST SLAG HEARTH
4 4 4 4 K C4 O 4 CO 4 IRON
F i g 4 .
BLAST FURNACE
1.
Zinc of fusion The lower portion where coke burns and produced carbon dioxide and a lot of heating is known as zone of fusion: C + O2 CO 2 DH = -406 kJ mol-1 Here the temperature is about 1775 K. A little above this, where temperature is above this, where temperature is about 1475 K - 1575 K, iron coming from above melts. Zone of heat absorption The middle portion (temperature 1075 K - 1275 K), CO2 rising up is reduced to CO with the absorption of heat: CO2 + C 2CO DH = 163 kJ mol-1 In this portion, limestone coming from above is decomposed and the resultant lime (CaO), which acts as flux, combines with silica (present as impurity-gangue) to form calcium silicate (fusible slag): CaCO3 CaO + CO2 CaO + SiO2 CaSiO3 Zone of reduction The upper portion (675K -975K) where iron oxide is reduced to spongy iron by carbon monoxide rising up the furnace: Fe2O3 + 3CO 2Fe + 3CO2 The reduction is believed to take place in stages: 3Fe2O3 + CO 2Fe3O4 + CO2 Fe3O4 + CO 3FeO + CO2 FeO + CO Fe + CO2
2.
3.
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MATALLURGY
At the bottom of the furnace the molten iron sinks down while above this floats the fusible slag which protects the molten iron form oxidation. These two can be removed from different holes (Fig. 4). Waste gases escaping at the top consists of about 30% CO, 10% CO2 and the rest nitrogen. Iron obtained from the blast furnace is known as pig iron. Pig iron contains about 2-5% carbon as well as other impurities (usually Si, Mn, S and P). Pig iron is converted into cast iron by remelting in a vertical furnace heated by coke. Cast iron expands on solidification and is used for casting various articles. Wrought iron, which is the purest form of iron, can be obtained by heating cast iron in a reverberatory furnace lined with iron oxide. Wrought iron contains about 0.2% carbon. Extraction of Tin. Metallic tin is extracted from tin stone which contains about 10% of the metal as SnO2 , the rest being siliceous matter, tungstates of Fe, Cu and As. After crushing, the ore is concentrated by washing in a current of water (Gravity process to remove lighter gangue particles) and by magnetic separator to remove tungstates of Fe and Mn. The ore is roasted to remove A and As their oxides. The ore then may be washed to remove sulphates of Cu and Fe. This gives black tin. Finally, the ore is smelted in a reverberatory furnace or in a blast furnace at 1475-1575K. The ore is mixed with one-fifth of its mass of powdered anthracite (coal) and little of lime or fluorspar which is used as flux. Tin oxide is reduced to tin: SnO2 + 2C Sn + 2CO The molten metal collected from the bottom of furnace contains impurities such as Fe, Pb, S and As. The metal may be purified electrolytically REFINING OF TIN (i) Liquation or sweating- When the block of impure tin is heated on the sloping hearth of reverberatory furnace tin, alongwith lead and bismuth (all having a much lower melting points than other metals), run off leaving dross, an alloy of Sn, Fe, Cu, W, As. (ii) Poling (stirring with logs of green wood) of this sweated tin is done. Impurities get oxidised & form scum which is skimmed off. 99% Sn is obtained. Scum & dross are repurified. Slag contains 10-25% Sn as SnSiO3 because of amphoteric nature of tin. This is recovered by smelting with carbon and CaO flux at a much higher temperature. SnSiO3 + CaO + C Sn + CaSiO3 + CO Electrolytic refining : Cathode-pure metal, Anode -pure tin, Electrolyte SnSO4(aq) with sulphuric acid and hydrofluosilicic acid. COPPER AND LEAD Both copper and lead may be extracted by self-reduction method. Extraction of Copper :Copper is mainly extracted from copper pyrites. After the concentration of its ore by froth flotation process, the ore is roasted in a current of air to remove arsenic, antimony and much of sulphur. The reactions occurring are (i) 2CuFeS2 + O 2 Cu2S + 2FeS + SO2 (major reaction) (ii) 2Cu2S + 3O 2 2Cu2O + 2SO2 (iii) 2FeS + 3O2 2FeO + 2SO2 (minor reactions) The ore is then mixed with a little coke and sand and smelted in a water-jacketed blast furnace. The minor reactions that occured during roasting continue here. Ferrous oxide combines with sand to form a fusible slag. Cuprous oxide formed combines with ferrous sulphide to give ferrous oxide and cuprous sulphide. This is because iron has more affinity for oxygen than copper. (iv) FeO + SiO2 FeSiO3 (v) Cu2 O + FeS Cu2S + FeO
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MATALLURGY
Molten mass collected from the bottom of furnace contains largely cuprous sulphide and a little ferrous sulphide. This molten mass is known as matte.
C o n v e r t e r
S i O -a i r 4
M o l t e n m a t t e F I G .4 B E S S E M E RC O N V E R T E R
The molten matte is finally transferred to Bessemer converter (Fig. 5). A blast of sand and air is blown in the converter through tuyeres which are situated a little above the bottom. This causes removal of S and As oxides and ferrous oxide as slag (reaction iv). At the same time Cu2 S is oxidized mostly into Cu2O (reaction ii) and partly into CuO and CuSO4. All these react with Cu2S giving copper. The reactions are (ii) 2Cu2 S + 3O2 2Cu 2O + 2SO2 2Cu2 S + 5O2 2CuSO4 + 2CuO 2Cu2 O + Cu2S 6Cu + SO2 CuSO4 + Cu2S 3Cu + 2SO2 Cu2S + 2 CuO 4Cu + SO2 Finally, copper may be refined electrolytically (electrolyte; copper sulphate: anode; impure copper and cathode; pure copper). Extraction of lead: Lead is mainly extracted from galena. After the concentration of the ore by froth flotation process, the ore is roasted in a reverberatory furnace for about six hours at a moderate temperature in a current of air. Part of galena is converted into lead oxide and lead sulphate. After this, the supply of air is stopped and small quantities of carbon, quicklime and cheap iron ore are added along with increase of temperature. At this stage, unreacted sulphide reacts with the lead oxide and sulphate giving metallic lead: PbS + 2PbO 3Pb + 2SO2 PbS + PbSO4 2Pb + 2SO2 The obtained lead contains impurities such as Cu, Ag, Bi, Sb and Sn. Silver is removed by Parkes process where molten zinc is added to molten impure lead. The former is immiscible with the latter. Silver is more soluble in molten zinc than in molten lead. Zinc-silver alloy solidifies earlier then molten lead and thus can be separated. After this, crude lead is refined electrolytically (Electrolyte; lead silicofluoride, PbSiF6 and hydrofluosilicic acid, H2SiF6 with a little gelatin, anode; crude lead and cathode; pure lead). MAGNESIUM AND ALUMINIUM Extraction of magnesium Magnesium is commonly obtained by the electrolysis of fused magnesium chloride containing a little (25%) sodium chloride and sodium fluoride at 700 0C in an airtight iron pot which itself serves as the cathode, the anode being a graphite rod which dips into the electrolyte. The anode is surrounded by a perforated porcelain tube for the exit of chlorine. The electrolysis is carried out in the atmosphere of coal gas so as to prevent the attack of atmospheric oxygen and nitrogen on magnesium. Molten magnesium being lighter then the electrolyte, it floats over
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MATALLURGY
the fused electrolyte and is withdrawn (Fig. 6). Voltage ~ 6V.

G r a p h i t e a n o d e
C l 4
P o r c e l a i n h o d o I n e r t g a s (o a lg a s ) c
I n e r t g a s
I r o n c a t h o d e M g M o l t e n e l e c t r o l y t e I r o n c l e l
FIG. 4 ELECTROLYTIC CELL FOR THE PRODUCTION OF MAGNESIUM

In Dow process, magnesium is recovered from seawater as magnesium chloride which is then electrolysed using cell described above (Fig. 6). Dows Sea Water Process. Sea water contains 0.13% Mg ions. Mg2+ (seawater) + Ca(OH)2 (from oyster shells) Mg(OH)2 + CaCl2 MgCl2.2H2O MgCl 2 . 2H 2 O MgCl 2 . 1.5H 2 O MgCl 2 Dows Natural Brine Process. MgCO3.CaCO3 MgO.CaO CaCl2 (aq)+ MgCl2(aq) MgCl2(aq) + CaCO3 (dolomite) (calcined dolomite) The reaction is : CaCl 2 . MgCl 2 (aq) + MgO.CaO + 2CO 2 MgCl 2 (aq) + 2CaCO 3 3 Electrolysis. Anhydrous carnallite (KClMgCl26H2O) may also be employed as the starting material of magnesium chloride. The cathode may be a layer of molten lead on the floor of the cell and anode may be graphite rods which are suspended above the molten lead. Magnesium liberated at the cathode dissolves in molten lead. The alloy of lead-magnesium is subjected to electrolysis to obtain pure magnesium (electrolyte: fused carnallite, anode-lead-magnesium alloy and cathode-steel rods.) Extraction of Aluminium Aluminium is isolated from the electrolysis of bauxite, Al2O3 2H2O. Since it is difficult to purify aluminium, bauxite ore is purified either by Baeyer's process (or Hall's process) or Serpek's process depending upon the impurity present in the ore. If the bauxite contains iron oxide as the impurity, one can use Baeyer's or Hall's process as described below. Baeyer's Process: Finally ground ore is roasted to convert ferrous oxide to ferric oxide and then digested with concentrated caustic soda solution at 423K. Al2O3 dissolves while Fe2O3 remains undissolved. The latter is filtered off and from the solution Al(OH)3 gives Al2O3. Al2O3 + 2OH- + 3H2O 2Al(OH)-4 Aluminate ion dissolves Al(OH)-4 + H+ Al(OH)3 + H2O precipitates heat 2Al(OH)3 Al2O3 + 3H2O Hall's Process: In this process the ore is fused with sodium carbonate when soluble meta-aluminate (NaAlO2) is produced. This is extracted with water leaving behind iron oxide. Carbon dioxide at 323-333 K is passed through water extract to get Al(OH)3 which on heating gives Al2O3. Al2O3 + Na2CO3 fused 2NaAlO2 + CO2 extracted with water
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MATALLURGY
2NaAlO2 + 3H2O + CO2 2Al(OH)3 + Na2CO3 2Al(OH)3 heat Al2 O3 + 3H2O If the impurity is silica, the Serpek's process is used to purify bauxite. Serpek's Process : The powdered ore is mixed with coke and heated to 2075K in a current of nitrogen. Silica present is reduced to silicon which volatilizes off and alumina gives aluminium nitride. The hydrolysis of the latter gives Al(OH)3, heating of which gives Al2O3. SiO2 + 2C Si - + 2CO2Al2O3 + 3C + N2 2AlN + 3CO AlN + 3H2O Al(OH)3 + NH3
Al2O3 + 3H2O 2Al(OH)3 heat ELECTROLYTIC CELL FOR THE PRODUCTION OF ALUMINIUM
At the cathode : Al3+ + 3e- Al At the anode: C(s) + 2O2- CO2(g) + 4eFIG. 7 ELECTROLYTIC CELL FOR THE PRODUCTION OF ALUMINIUM
After obtaining pure Al2O3, it is dissolved in fused cryollite, Na3AlF6, with a little fluorspar, CaF2 and is electrolysed in an iron tank lined with blocks of carbon which serve as the cathode. The anode consists of a number of graphite rods suspended vertically inside the tank (Fig. 7) Aluminium gets settled at the bottom of the tank and can be removed. The reactions occurring at the electrodes are Cathode Al3+ + 3e- Al 2Anode 2O 2 O2 + 4eC + O2 CO2 Anode is replaced periodically because of its consumption. SILVER AND GOLD Cyanide Process: Silver and gold are extracted by the cyanide process (MacArthur-Forrest process). After the preliminary crushing and concentration by froth floatation process, the ore (crushed auriferous rocks in the case of gold)is leached with dilute (0.4-7%) solution of sodium cyanide made alkaline by adding lime kept agitated by a current of air. Silver (or gold) pass into solution as argentocyanide (or aurocyanide) : Ag2S + 4NaCN l 2Na[Ag(CN)2] + Na2S The air blown in remove Na2S as Na2S2O3 and Na2SO4 causing the above reaction to proceed to completion. 2Na2S + 2O2 + H2O Na2S2O3 + 2NaOH Na2S2O3 + 2NaOH + 2O2 2Na2SO4 + H2O 4Au + 8NaCN + 2H2O + O2 l 4Na[Au(CN)2] + 4NaOH The solution obtained above is filtered and treated with scrap iron or zinc when silver (or gold) get precipitated: 2Ag(CN)-2 + Zn Zn(CN)2-4 + 2Ag 2Na[Au(CN)2] + Zn Na2[Zn(CN)4] + 2Au The obtained silver is purified electrolytically (electrolyte:silver nitrate solution containing 1% nitric acid, anode: impure silver and cathode: pure silver). The impurities like zinc and copper pass into the solution while gold falls down as anode mud. Gold thus obtained is contaminated by zinc which is dissolved out by sulphuric acid. The dried residue of gold is then fused under borax (flux) in graphite crucible and the melted down gold (bullion) which invariably contains silver, is sent for refining.
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MATALLURGY
MET ALL UR GY A T A GL AN CE METALL ALLUR URG AT GLAN ANCE
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MATALLURGY
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Bansal Classes Metallurgy

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MATALLURGY

Carnallite, MgCl2KCl6H2O Epsomite(epsom salt), MgCO37H2O Kainite, MgSO4KCl3H2O

CONCENTRATED ORE GANGUE

OIL WATER MIXTURE

Fig.1 MAGNETIC SEPARATION

MgO + CO2 ZnO + CO2 FeO + CO2

(b) Partical oxidising or sulphating

Smelting: * Concentrate ore (ore + gangue) + RA (carbon) + Flux

Na+ + Cl (Ions become mobile)

WASTE GASES 4 4 4 K 4Fe4O4 4 CO 4Fe4O4 - CO4

CaCO4 CaO 4 CO4

Fe4O4 4 CO 4FeO 4 CO4 4 4 4 4 K C4CO4 4CO FeO 4 CO Fe(S) 4 CO4 4 4 4 4 K e l t s I m p u r ei r o nm M o l t e ns l a gf o r m s 4 4 4 4 K

HOT AIR BLAST SLAG HEARTH

the fused electrolyte and is withdrawn (Fig. 6). Voltage ~ 6V.

FIG. 4 ELECTROLYTIC CELL FOR THE PRODUCTION OF MAGNESIUM

MET ALL UR GY A T A GL AN CE METALL ALLUR URG AT GLAN ANCE

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