Natural Sciences Tripos Part III MATERIALS SCIENCE M3: Extraction and Recycling

Student Edition

Dr. R. V. Kumar
Michaelmas Term 2011-12

Part III Materials Science

M3 Extraction and Recycling Michaelmas 2011 (12 Lectures) Dr RV Kumar

Course Synopsis
Introduction to metal production and recycling; statistics Routes to iron & steelmaking - blast furnace; thermodynamics of liquid iron alloys; dilute solutions; alternate standard states; interaction parameters; metal-slag equilibria; desiliconisation of iron; slag basicity; ionic theory of slags; desulphurisation; basic oxygen steelmaking; refining reactions in steel; dissolution of oxygen, nitrogen and hydrogen in liquid steel; deoxidation of liquid steel; electric arc furnace steelmaking; secondary steelmaking; stainless steel production Extraction of copper; hydrometallurgical route and electrowinning of copper; pyrometallurgical route; flash smelting; converting; and electrorefining Extraction of aluminium; Bayers process; Hall-Heroult Cell for electrowinning aluminium from a molten salt Titanium production using the Kroll process Recycling issues for the future and new technological opportunities - Case studies

Relevant Textbooks/Internet Resource

1. Chemical Metallurgy - JJ Moore (Butterworth) 2. Fundamentals of steelmaking metallurgy - B Deo and R Boom (Prentice Hall International) 3. Extraction of Copper By WG Davenport et al 4. Department of Materials Science & Metallurgy Web page link: www.msm.cam.ac.uk/Teaching/ follow links through Undergraduate Teaching / Other Resources and Link / MATTER/ Selection from a list of on-line resources for Materials Science/ steeluniversity.org (A range of topics available from Site Contents) 5. Department of Materials Science & Metallurgy Web page link: www.msm.cam.ac.uk/Teaching/PartIII/M3/M3H.pdf 6. Link for Interactive Ellingham diagram: www.doitpoms.ac.uk/tlplib

METAL PRODUCTION
The current annual world production of metals exceeds 1.5 billion tonnes. This staggering production rate is a relatively modern phenomenon. It took all the time from antiquity to 1900 to achieve a total cumulative world-wide production of one bt of all metals. In the 1st half of the 20th century, a bt of metal was being produced each decade on average. In the 80s and the 90s the annual production had reached a nearly constant rate at a bt per year. In the 1st decade of this millennium, metal production began to rise again reaching an annual rate of 1.4 bt in 2007 and has remained more or less constant since 2008 and is expected to rise again towards 2 bt by 2020. Iron & steel constitute over 90 % of all metals produced each year. In order to achieve the 1.3 billion tonnes of steel production in the current year, over 1.6 b tonne of iron ore (hematite or magnetite) is transported around the world from few selected areas, making iron ore the largest traded commodity in the world. Of the total steel produced, nearly 600 million tonnes per year arises from discarded steel scrap, making steel the most recycled industrial material. The gross market for raw steel alone is over 700 billion per year. Steel constitutes a vital raw material in a wide variety of applications in automobile, road, rail and sea transportation, construction, architecture, appliances, packaging, power & energy, agricultural and earth moving equipment and numerous structural and engineering areas. Around 35 million tonnes of aluminium is produced each year from hydrated alumina bauxite ores, while another 16 million tonnes are recovered by recycling discarded aluminium products. The gross market for raw aluminium is over 100 billion per year. Aluminium is used in transportation, construction, beverage cans, electrical wiring, packaging and many structural applications. Copper is produced in amounts greater than 20 million tonnes each year, with over 75 % using pyrometallurgical route and the remaining 20+ % by the hydrometallurgical route, with all the new plants using the latter approach. Copper is extensively used in electrical applications, piping & tubing; coinage; and many engineering applications. Titanium production is currently at 60,000 tonnes per year, used predominantly in the aerospace industry and in chemical plants with new applications emerging in biomedical field and the high-end automobile use. If a substantial reduction in the cost of Ti could be achieved, annual production could approach 250,000 tonnes per year by the end of this decade. In the UK, the per capita consumption of steel is nearly 500 Kg per year. In comparison, all the other metals together add up to 25 Kg per person per year, while paper and plastics the two other major industrial materials are each consumed at the rate of around 100 Kg per person each year.

STEEL PROCESSING OVERVIEW

Ironmaking Iron ore, coke and lime are raw materials fed into the blast furnace (BF) to produce Csaturated (4 4.5 wt %) liquid iron (called hot metal). Of the over 1 btpy of iron ore used, 10 % of the ore is reduced by natural gas in the solid state to a spongy iron called the direct reduced iron (DRI). Steelmaking The basic oxygen steelmaking (BOS) process takes the liquid hot metal from the BF and combines with up to 20 wt % of recycled scrap steel to decrease the C content to between 0 to 1.5 wt % by blowing pure oxygen through the liquid metal in a special converter to produce steel. Over 500 mtpy of steel is produced by BOS. Alternately, the electric arc furnace (EAF) is used to remelt recycled scrap steel along with DRI to produce nearly 400 mtpy of steel by this route. Secondary Steelmaking A range of controlled processes are applied to both the BOS and the EAF steel to make fine adjustment to the steel composition, temperature and cleanness. Casting The steel is then continuously cast (CONCAST) into solid slabs, blooms or billets. The primary shapes are then subjected to further forming processes such as hot rolling, cold drawing, wire drawing, machining (e.g. drilling), joining (e,g. welding), coating (e.g. galvanizing), heat treatment (e.g. tempering) and surface treatment (e.g. carburising).

THE IRON AND STEELMAKING PROCESS The BF - BOF Route The Iron Blast Furnace:
Reduction smelting of iron ore (lumpy, sinter or pellet) with metallurgical coke to produce a crude liquid iron called hot metal and separation of the gangue from the metal by reacting gangue with a flux (lime-based) to form a slag

The Iron blast furnace is a tall refractory lined steel shell with a circular cross-section (Height up to 30m and diameter up to 10m) The stack is filled with a controlled mixture of iron ore, coke and flux A hot blast of air ( at >1000K) is injected through water cooled Cu nozzles (tuyueres 12-24) distributed across the cross-section above the hearth

Raw Materials: Lumpy iron ore + agglomerates (sinters or pellets) - modern practices use 100% fully fluxed agglomerates Coke - produced in coke ovens by heating special grade coal in absence of air Flux - limestone, dolomite or lime in fluxed agglomerates to form slag with gangue in the ore and coke ash Hot blast of air (with 2-5% excess oxygen) to burn the coke Auxiliary fuels (with hot blast) such as oil, coal dust or natural gas to decrease the coke rate

Products: Hot metal - C-saturated iron ( typically 4.3% C, 0.8% Mn, 0.7% Si, <0.05% S & P) Slag - CaO(45%), MgO(5%) (flux); SiO2(35%), Al2O3(12%), MnO(2-3%), S (1-2%)(from iron ore and coke ash) - used as aggregate in construction BF gas - 25%CO, 2%H2, 2%H2O, 17%CO2 and 56% N2 - used as a low grade fuel within the steel plant Flue dust - from top gas in dust catchers (oxides of Fe, Zn, Na, K)

DILUTE SOLUTIONS IN MOLTEN IRON Liquid iron & steel form dilute liquid solutions of Fe and various alloying elements and impurities of elements such as C, Si, Mn, O, S, P, H, N, Al, V etc. These elements arise from natural sources such as iron ore (Si, Mn), Coke (C, Si, P, S), atmosphere (O, H, N) or as additives (Al, V, Ti, Nb) in small quantities. Consider the situation when an element or its oxide is not pure, but in solution, e.g. Si dissolved in iron and SiO2 dissolved in the oxide slag (solution of molten oxides) and the iron is in equilibrium with the slag: Si + O2 (g) = (SiO2) Notation: Si refers to a dilute solution of Si in molten iron and (SiO2) refers to silica in the slag phase The standard free energy change at any given temperature remains unchanged as does the equilibrium constant; however the activities of both silicon and its oxide must be considered: K = aSiO2 / aSi pO2 In the Raoultian standard state for Si, pure Si at the temperature of interest is assigned an activity = 1. At any molar fraction, aSi = Si Xsi where = activity coefficient and X = mole fraction

Alternate Standard State The thermodynamic treatment of dilute liquid solutions is greatly simplified by Henrys law according to which as Xi 0 ; the activity coefficient i io (constant) i.e., activity vs composition is a straight line in very dilute solutions The 1 wt % Standard State: It is more convenient to express concentrations in wt % rather than mole fractions for dilute solutions. Therefore a new standard state has been formulated which is called the 1 wt % Standard State. The activity in this state is written as h (rather than a) and h of an element = 1, when the concentration of the element = 1 wt % expressed as: hi = 1 when concentration of i in Fe = 1 wt % The Raoultian standard state defines ai = i Xi where = activity coefficient and X = mole fraction For a dilute solution: i io (constant) and Xi = 0.558 (wt % i)/ Mi therefore, the relationship between the Raoultian and the 1 wt % standard state is: ai = io (0.558 / Mi) hi The exact limit of validity of Henrys law in any dilute solution is not theoretically deducible and therefore a correction factor is introduced: hi = fi (wt % i) where fi is called the Henrian activity coefficient

Effect of change of standard states on Free Energy Calculations It is straightforward to change the standard state from Raoultian to 1 wt % and account for this change in the free energy of that component: In the Raoultian standard state: In the 1 wt % standard state: Gi = GiO,R (Xi = 1) + RT ln ai Gi = GiO, 1wt % (wt % of i= 1) + RT ln hi

Thus GiO, 1wt % (wt % of i= 1) - GiO,R (Xi = 1) = RT ln ai /hi = RT ln io (0.558 / Mi) A given reaction must clearly specify the standard states used for a given component in that reaction. The default position is for gases the standard state is pure gas at 1 am pressure; for Raoultian standard state, it is pure solid or liquid component in its stable form. The 1 wt % standard state is specified explicitly by stating (1 wt % ) and/ or by underlining the component, e.g.: Si (1 wt %) + O2 (g) = SiO2(s) All three standard states are used in the above reaction and therefore the free energy change of the above reaction should be adjusted w.r.t to the normal standard states for Si in Fe. Thus GO = - RT ln K and K = aSiO2 / pO2 hSi and hSi = fSi (wt % Si) Interaction Parameters: In liquid steel containing many solutes, the henrian activity coefficient of a component is affected by the presence of other alloying elements. The interaction effects are simply derived using the linear terms in a Taylors series expansion: log fi = ( log fi / wt % j) (wt % j) = eii (wt % i) + eij (wt % j) + ..

Thermodynamics of Carbon Dissolution Solubility of C in liquid iron is given by the function: wt % C = 0.56 + 0.00257 T When iron is saturated with C the melt is often called the hot metal. In hot metal the Raoultian standard for carbon is more convenient as under saturated condition the Raoultian activity is equal to 1. aC = 1 In dilute solutions as in liquid steel, it is common to use the 1 wt % standard state. The Henrian Constant of C in liquid Fe is: CO = 1180/T - 0.8 The solubility of carbon in iron is affected by the presence of other elements such as Si, P, S and Mn.

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Metal-Slag Equilibrium A solution of molten oxides is called Slag. The purpose of slag in metal extraction and refining is to collect al the gangue waste products in the form of oxides (or sulphides in small quantities) and separate the impurities into a separate phase often of lower density which can thus float on top of molten metal for easy separation. Thus refining reactions are often studied in terms of the relevant metal-slag equilibrium. The thermodynamics of the refining behaviour of a slag phase with respect to a liquid metal is a function of temperature and of the composition of the two phases. Molecular Theory of Slags and Desiliconisation An example of slag-metal-gas equilibrium is the distribution of Si between the liquid iron (e.g. C saturated hot metal) and the molten slag phase {denoted by using a bracket , e.g. (SiO2)}: (SiO2) + 2 Csaturated = Si (1 wt %) + 2 CO(g) GO = - RT ln K where K = hSi pCO2 / aSiO2 hence the distribution of Si between the slag and the metal can be expressed as: XSiO2 / wt % Si = fsi pCO2 / K SiO2 To achieve relatively high value of Si in the slag and low in the liquid iron (typically < 0.4 wt %), called desiliconisation from iron, requires: low K (requires low temperature for this endothermic reaction) low SiO2 (requires high CaO or such basic oxides) high fSi (function of iron composition) high pCO (determined by the process conditions) The first two requirements are in conflict, as a slag containing too high a mole fraction of CaO results in raising the liquidus temperature of the slag requiring higher operating temperature to keep the slag molten, which in turn increases the value of K. (A slag too rich in SiO2 also has a high liquidus temperature). Both conditions would result in a high Si in the hot metal. There is an optimum composition at which the liquidus temperature in the CaO-SiO2 is the lowest which promotes desiliconisation.

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Slag Basicity The slag composition is often expressed as ratio of CaO and SiO2. XCaO / XSiO2 = 2 gives the lowest operating temperature It is more common to express this ratio in terms of wt % rather than mole fraction for practical convenience and is defined as the basicity of the slag. Basicity = wt % CaO / wt % SiO2 A slag may contain several other acidic oxides such as Al2O3, P2O5 and Fe2O3 (network formers) and several other basic oxides such as MgO, FeO and MnO (network modifiers) and it more accurate to define the slag basicity as: Basicity = wt % of all basic oxides / wt % of all acidic oxides In summary in the molecular theory of slags, the molten slag is assumed to be a solution of simple molecules such as CaO, MgO, SiO2 etc. and the distribution of key elements in the production and refining of iron and steel such as Si, S and P will depend upon the temperature and the respective activities in the metal and the slag phase. Desulphurisation Consider removal of S from C saturated iron to a slag containing CaO: S (1 wt %) + (CaO) + Csatd = (CaS) + CO(g) For the above endothermic reaction: K = aCaS pCO / fs (wt % S) aCaO The distribution of S between the slag and the metal phase is : XCaS / wt % S = K fs aCaO / CaS pCO As T increases, the value of K increases and desulphurisation is promoted. High CaO also helps the removal of sulphur. High CaO implies the need for a high operating temperature. Thus desiliconisation and desulpurisation reactions from a carbon saturated iron to a slag phase are in conflict with each other and the resolution of this is critical in ironmaking - the precursor step to steelmaking

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IONIC THEORY OF SLAGS In the ionic theory of slags, basic oxides are those which can completely dissociate to supply oxygen ions: CaO = Ca2+ + O2MgO = Mg2+ + O2MnO = Mn2+ + O2FeO = Fe2+ + O2The oxygen ions can break up (depolymerise) the network formed by acidic oxides such as SiO2, Al2O3, P2O5 and Fe2O3. Such reactions can be written as: SiO2 + 2 O2- = SiO44P2O5 + 3 O2- = 2PO43Al2O3 + 3 O2- = 2AlO33In a CaO-SiO2 system, the full depolymerisation of the silica network requires 2 moles of CaO to react with 1 mole of SiO2 to form a slag which is neutral i.e. all the free oxygen ions are used up. In a basic slag there is excess of CaO such that free oxygen ion are available. In an acidic slag, there are insufficient free oxygen ions to break up the full network. Both the acidic and basis slag have high viscosity while the neutral slag has the minimum viscosity. Basicity of an oxide slag = NO2- = nO2- / nanions Any CaS in the slag is also dissociated: CaS = Ca2+ + S2-

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Flux:
Basic oxides flux the acidic oxides - in order to flux Al2O3 or P2O5 requires much higher concentration of CaO. The activity of any oxide is written in terms of its ionic components: aCaO = Nca2+ NO2where Nca2+ = nCa2+ / ncations Within the basic oxides, CaO is more basic than MgO, which in turn is more basic than MnO and FeO. It is determined by the magnitude of difference in the electronegativity of the cation with respect to the anion.

Example of Dephosphorisation Reaction in the Ionic Theory: 2 P (1 wt %) + 5 O (1 wt %) + 3 O2- = 2 PO43Therefore the equilibrium constant K = NPO4(3-)2 / hP2 hO5 NO(2-)3 In order to maximise dephosphorisation from Fe (l) to the slag phase, it is necessary to maximise the ratio: NPO4(3-)2 / hP2 = K hO5 NO(2-)3 which requires high value of K (lower temperature) , high CaO, high basicity and high oxygen concentration in the liquid iron. In the blast furnace, it is normal to use low basicity and a relatively low CaO concentration to promote disiliconisation. The oxygen content in the C-saturated Fe is also very low, thus dephosphorisation is not achieved in the BF. All P is removed during the steelmaking stage in the BOF. External Desulphurisation of Hot Metal In order to minimise the coke rate, BF tend to operate with a neutral slag, promoting the formation of a fluid slag at relatively low temperatures. Higher productivity, lower flux consumption and lower slag volume is produced. These conditions also promote desiliconisation (Si < 0.7 wt %), at the expense of high S ( > 0.05 wt %). It is difficult to remove S effectively in the steelmaking stage. Given that S is very harmful to steel, it is required to be removed. Therefore S is removed external to the BF enroute to BOF in External Desulphurisation stations in ladles or torpedo cars in batches of 300-500 tonnes, by reacting hot metal with Mg, CaO and CaC2 which are injected in for 5-20 minutes.

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The Basic Oxygen Furnace (BOF)

Refining in the BOF consists of removing impurities by oxidation with pure oxygen which provides the heat required; a basic flux (CaO) is used to remove Si, Mn, P and some S; C is removed as CO in the gas phase Oxygen at supersonic velocities impinge upon the hot metal, oxidising the various elements, producing slag, gases (CO) and heat Excess heat is available to melt 20 - 25% of charge as cold scrap Reactions are vigorous, causing the metal/slag/gas phases to form an emulsion and a foam, thus achieving rapid reaction rates (20-30 minutes for 150-400 tonnes of steel) As C is eliminated, the m.p of iron increases, but heat input from oxidation keeps the bath molten Oxidation of C, Si and Mn more favourable than that of Fe (Ellingham Diagram) and hence easy to eliminate from steel; considerable amounts of Fe is also oxidised (iron loss) Oxidation of P is less favourable and requires a dramatic decrease in the activity of the product P2O5 in the slag phase to achieve dephosphorisation of steel; in a slag with high basicity, the activity can be reduced to < 10-20 The final average composition of steel after BOS: C & Si - 0-0.2%; Mn - 0.15%; P & S each < 0.05%, perhaps as low as 0.015%); O - 0.04 to 0.08% At this stage the O content is too high and is adjusted in the ladle after tapping steel by deoxidising with Si, Mn, Al or Ca (or any combinations) to form stable oxides which can float out before casting

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Thermodynamics of Dissolution of Oxygen in Iron Dissolution of oxygen in molten iron is represented by: O2 (g) O (1 wt % standard state) GO (kJ) = -117.3 -0.002889 T and thus: hO = log pO2 + 6126/T + 0.15 = fO (wt % O) eOO = -0.2

In the binary Fe-O(l) system

Furthermore the maximum solubility in pure liquid iron is determined by: Fe(l) + O (1 wt %) = FeO(l) for which (m.p. of FeO is 1651K)

log K = -6372/T + 2.73 = log (hO)saturated

Refining Reactions in the BOF Decarburisation Removal of C from 4.3-4.5 wt % (saturated level) to 0.01 to 0.2 wt % (C in the range of 0.2 to 1.5 wt % is also produced infrequently) C + O = CO(g) Log K = -1167/T 2.07 hC hO = 0.002 at 1873 K for pCO = 1 atm. Both temperature and pressure influence the decarburisation reaction. As decarburisation proceeds, the m.p. of Fe-C system increases, while the temperature of the melt increases due to heat of reactions such that the metal remains molten. The wt % O in the melt increaes as does FeO in the slag. Some of the FeO in the slag is directly oxidised to Fe2O3. The oxidising power of the slag is key to the refining reactions for controlling not only C but also Si, Mn, P, S and O. C is the single most important alloying element for steel. Ultra low C Low C C wt% < 0.01 < 0.2 Treatment Quenched Annealed, normalized Strength High Medium Toughness High High Fabrication Good Excellent Application Sheet Structures (auto, pipe) and sheet

Medium C 0.2 to 0.8 Quenched, tempered High High Good Shafts, gears rails, rods

High C 0.8 1.5 Quenched, tempered V hard Low Fair Springs, tools, dies

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Thermodynamics of Nitrogen Dissolution in Iron The dissolution of nitrogen in iron is represented by: N2 (g) N (1 wt % standard state) The solubility is often expressed as Sieverts law: (wt % N) = k (pN2) where, K = -255.6/T - 1.26

The solubility of nitrogen in liquid steel at 1873 K in equilibrium with air is 0.035 wt %.

Thermodynamics of Hydrogen Dissolution The reaction to consider is: H2 (g) H (1 wt % standard state) The solubility is often expressed as Sieverts law: (wt % H) = k (pH2) where, K = -1670/T - 1.68

The solubility of hydrogen in liquid steel at 1873 K is typically 0.002 wt % . Deoxidation of liquid steel At the end of refining in the BOF, molten steel is typically at 1873-1900K and contains 0.04 - 0.08 wt % oxygen. During subsequent cooling, O can react with CO to form blow holes and porosity in solid steel. Some of the O may react with Fe to form FeO which can cause hot shortness during hot rolling and heat treatment. Thus O is often removed by deoxidation by using Al.

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BF BOS route, the Capital cost is very high, but reasonable for the EAF steelmaking route Cold scrap (and/ or DRI) melted and refined in EAF plants of typical sizes between 50,000 to 250,000 tpy (although there are EAFs as small as 10,000 tpy and as large as 1 mtpy)

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Secondary Steelmaking
At the end of BOS or EAF processing, steel needs further refining to add value by enhancing quality in a series of steps referred to as Secondary Steelmaking These may consist of Deoxidation, Desulphurisation, Degassing (for removal of H, N, O and C), inclusion engineering, microalloying, and Temperature control before CONCAST. Deoxidation: Al, Si, and Mn are the most common deoxidisers used in steelmaking. Mn is a mild deoxidiser but when combined with Si, can lead to the precipitation of Mn silicates which are molten in liquid steel at 1873 K and can be removed to a large extent from the steel by flotation. Although Al is a powerful deoxidiser, presence of alumina or aluminate inclusions reduces the fatigue resistance. Fatigue is very important in critical applications such as bearing steels and tire reinforcement wire and for such applications, steel is deoxidised by Mn-Si alloys. Al additions can produce very low levels of oxygen in steel ( < 10 ppm). Rate of deoxidation if often very low, but can be enhanced by stirring time. Alumina inclusions form dendritic structures which can act as stress raisers in steel during application. The solid inclusions also block the nozzle during CONCAST. It is common to use Ca-Al alloys as deoxidisers to achieve more rapid deoxidation rates. At the appropriate CaO/Al2O3 ratio, the calcium aluminates are in liquid state at the secondary steelmaking temperature which can help avoid the nozzle blockage problem in CONCAST and also to improved deoxidation rates and more acceptable morphology of remaining inclusions in solid steel. Desulphurisation Sulphur is detrimental to ductility, toughness, formability, weldability and corrosion resistance of steel (but beneficial to machinability). Normally sufficient Mn is added to steel to prevent the formation of FeS, which is highly detrimental to hot working leading to hot shortness. MnS can prevent hot shortness, but is more plastic during hot rolling than the steel matrix resulting in severe deformation into long stringers which act as crack initiation sites. The S specification ranges from 0.3 wt % for high machinable steels to < 0.07 wt % for crankshaft, 0.005 wt % for car wheel, and < 0.001 wt % for linepipe and aircraft steels. In best practice the S content of BOS or EAF is in the 0.01 0.02 wt %; this requires further desulphurization for many applications. Ca-Al alloy used for modifying the oxide inclusions can help desulphurising provided the oxygen content of the steel is deoxidised to very low levels (in the ppm range). MnS inclusions are replaced by harder CaS globular inclusions.

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Degassing Process: The most usual forms are Tank degassing and Recirculation Degasser where steel is subject to vacuum and Ar stirring. These result in the removal of hydrogen, nitrogen, oxygen and carbon. In practice, modern degassers attain pressures down to about 0.001 atm. Hydrogen content of 1-2 ppm can be achieved. The solubility of nitrogen in steel is very high in EAF steels. It is also increased significantly in any steel at the end of desulfurization process. N can be controlled to < 10 ppm by degassing. At low pressures, the C and O reaction to form CO is highly favoured. C and O can both be simultaneously removed in the ratio 12:16 as determined by their respective atomic masses. It is possible to produce steels with C < 0.001 wt % while simultaneously achieving O at < 0.0005 wt %.

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Extraction of Copper
Hydrometallurgical Route Hydrometallurgical methods treat ores/concentrates with aqueous solutions. These are extremely suitable for oxide ores, especially for very lean ores (<0.5%); steps consist of leaching with sulphuric acid, purification (e.g. solvent extraction) and electrowinning. Currently 25 % of copper extraction utilises hydrometallurgy, in fact all the new plants in the last 10 years are based on this approach. ELECTROWINNING Extraction of metals from aqueous solutions or molten salts in electrochemical cells the metal is plated or deposited on to the cathode (-ve), while the anode is an insoluble conductor(e.g. a Pb alloy), where a gas such as oxygen or chlorine is evolved From Aqueous Solutions electrochemical cell: At cathode: At anode: Copper sulphate in aq. Solution is decomposed in an

Cu2+ +2e = Cu H2O = 1/2 O2 + 2H+ + 2e

EO = + 0.34 V + RT/2F ln [Cu++] EO = + 1.23 V - RT/F pH

Net reaction for electrowinning copper is: CuSO4(aq) + H2O = Cu + 1/2 O2 + H2SO4(aq) G = 221.6kJ; E = -1.2V

1.2V is the minimum potential required to bring about the electrochemical reaction as shown above. Due to polarisation processes the operating voltages are nearly 2.5 V at a typical current density of 200 A/m2. The actual potential required is = 1.2 + A + C + IR

Note: Electrolytic extraction from aqueous solutions is possible for Ni, Co, Cd, Fe,
Zn and Mn, by decomposing their salts in aq solutions without the danger of decomposing H2O to form hydrogen gas at the cathode If the reversible electrode potential required to deposit a metal is < - 1 V (or Total potential > 3 V), the possibility of evolving hydrogen at the cathode increases

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HYDROMETALLURGICL ROUTE

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Pyrometallurgical Route
90% of world's primary copper originates in sulphide ores (0.5 to 2%Cu) - e.g. chalcopyrite (CuFeS2) and are not readily treated by hydrometallurgical methods; pyrometallurgical methods combined with electrochemical refining are used The sulphide ores are concentrated by froth flotation, by which copper minerals are selectively attached to air bubbles (reagents are added to render copper minerals hydrophobic, while the gangue are left water avid) rising through an aqueous pulp of ground ore (-100 ). Typical copper concentrates contain 20-30% copper, which are subjected to Flash Smelting

FLASH SMELTING
Flash smelting is carried out at controlled oxygen potentials with a suitable flux to produce a molten matte from concentrates separated from an immiscible slag The composition of matte is: 35-65% Cu; rest Fe and S; melting point: 1050-1130 oC; liquid density at 1200oC: 4.1 to 5.2 g/cc; The composition of matte smelting slag is: Fe (as oxides) - 30 to 40%; silica (from fluxes and recycled slags) - 35 to 40%; alumina and lime - up to 10% each; liquidus temperature: 1150-1200oC; density at 1200oC - 4.1 to 5.2 g/cc

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PYROMETALLURGICAL ROUTE

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Flash Smelting Reaction:

2CuFeS2 (conc.) + 2.5 O2 (g) + SiO2(flux) = Cu2S-FeS(matte) + FeO-SiO2(slag) + 2 SO2(g)

Autogenous Process A considerable amount of sulphur dioxide gas is produced (at conc. >10%), which can be recovered as liquid SO2 or as sulphuric acid Matte grade (% Cu in the matte): 35 - 65% A low matte grade higher productivity in smelting but matte has too much FeS leading to lower productivity in converting A high matte grade high copper losses in the slag but too little FeS which is the main fuel for subsequent processing

Two major types of Flash Smelting processes are available: 1. The Outokumpu process (>30 such furnaces in operation worldwide): Uses air (pre-heated or oxygen enriched) as oxidant + some auxiliary fuel if required; Lower sulphur dioxide content in the off-gas but can be converted to sulphuric acid; Matte grade up to 50 % and can be increased to 70 % using enriched air 2. The INCO process: (10 in operation worldwide): Uses pure oxygen as an oxidant; High conc. of sulphur dioxide in the off-gas; Flexible w.r.t matte grade as fuel / oxygen ratio can be varied A number of other processes are available such as Bath Smelting Processes (IsaSmelt or Ausmelt) A single vertical lance for injecting oxygen and fuel is submerged in the melt: (At least 5 in operation with potential to grow)

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MATTE CONVERTING
Converting of sulphide matte involves blowing air through the liquid matte in order to preferentially oxidise the more reactive metal sulphide; for example FeS is oxidised out of a Cu-Fe sulphide matte to form iron oxide which is fluxed with silica and lime to form a slag Copper metal is produced by a mutual reduction between copper sulphide and copper oxide Heat required to keep the metal and the slag phase in molten state is provided by the oxidation of FeS, which is the main source of energy in converting Converting is carried out in a Pierce-Smith converter in which air is side-blown; bottom blowing will chill the whole process as soon as FeS is oxidised in the bottom layer. Pierce-Smith converter is a horizontal basic refractory-lined cylindrical converter, with a gas collector Molten metal is charged through the mouth and the air is blown along the length of the vessel Preferential oxidation of FeS and other impurities such as ZnS, MnS take place: 2FeS (matte) + 3O2 (g) = 2FeO (slag) + 2SO2(g) H -250 kcal

Since FeO is more stable than Cu2O, any copper oxide formed is reduced back to the matte (see Ellingham diagram for the oxidation of sulphides) Acid Flux Silica is added to react with FeO to form a fluid slag, which is poured out of the converter, leaving virtually pure Cu2S melt, which is finally converted to molten Cu through mutual oxidation-reduction reaction Au, PGM and sulphides of Pb, Ni and Ag are not oxidised to the slag, but retained in the matte

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Reactions in the final stages of Matte Converting:

2Cu2S (matte) + 3O2 (g) = 2Cu2O (slag) + 2SO2(g) Cu2S (matte) + 2Cu2O (slag) = 6Cu(l) + SO2(g) ------------------------------------------------------------------------Net Reaction: Cu2S (matte) + O2 (g) = 2Cu (l) + SO2(g) H -50 kcal The reaction is exothermic enough to supply all the heat required for converting matte to Cu Bubbling of the gaseous product through the melt produces a blister effect hence the product is called "blister copper" SO2 is a by-product at concentrations > 5% in the off-gas can be easily converted to sulphuric acid, it is a serious pollutant and a nuisance in copper production

Continuous Processes (Mitsubishi Process - 5 plants worldwide)

The process is based on using three interconnected reactors so that copper concentrate is converted to copper in one continuous process in multi-steps.

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FIRE REFINING:
Blister copper is too high in residual S and O, to directly cast into anodes for electrorefining (O: 0.5 - 0.8%; S: 0.1%) as S and O can combine to form SO2 on solidification, producing a blistering effect (poor mechanical properties) S and O are removed by fire refining in two stages: Stage I: Air is injected into molten blister copper for removing S as SO2 Stage II: Hydrocarbon is injected to remove excess O as CO and H2O Fire refined copper is cast into strong, flat thin anode plates for electrorefining

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ELECTROREFINING:
Electrorefining of copper anode consists of applying an electrical potential between the copper anode (+ve) and a starter sheet (pure Cu, stainless steel or Ti) as the cathode, both immersed in a cell containing an acidified CuSO4 solution Overall Cell Reaction: Cu (anode) = Cu (cathode) G = 0 and Emin = 0 V

E(actual) = 0.3V to overcome the resistance of the electrolyte and the external circuit + overpotentials to carry out the reactions at reasonable rates Typically, I = 200 A/m2 and Energy consumption = 300 KWH per tonne of Cu deposited Au, Ag, Pt and other precious metals do not dissolve in the electrolyte and are collected in the anode slimes S, Se, Te, Pb and Sn are also collected in the anode slimes As, Bi, Co, Fe, Ni and Sb dissolve in the electrolyte, but do not deposit in the cathode and are removed by purification of the electrolyte

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ELECTROWINNING OF ALUMINIUM: Reactive metals such as Al, Mg, Li, Ca, Na, K etc cannot be deposited from their salts in aqueous solutions but are deposited from their fused salts Bauxite ore is purified in Bayer's process by leaching with NaOH(aq) in order to produce pure Alumina for electrowinning Al Alumina can be dissolved upto 8% in a fused salt of cryolite NaFAlF3 at 1273K and electrochemically decomposed: Al2O3(l) = 2Al(l) + 3/2 O2 (g) G (1273K) = 1279 kJ E(min) = -2.2V The molten electrolyte is covered with a crust of alumina which acts as a reservoir of feed as well as insulation Both the anode and the cathode is made up of graphite - the graphite anode consumed during the process as a result of oxidation with oxygen evolved at the anode, which leads to a reduction in the min. potential required: Al2O3(l) + 3/2 C = 2Al(l) + 3/2 CO2 (g) for which G (1273K) = 686 kJ E(min) = -1.18 V; E(total) = 6 V (due to and IR losses) Primary Al production is a power intensive process (17 KWH/Kg of Al)

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Production of Ti by the Kroll Process

Although it is thermodynamically feasible to reduce TiO2 by C at elevated temperatures, a metallic product is not obtained as Ti forms stable carbides with C. Thus C based reduction is not a suitable option for producing Ti metal. Metallic reagents such as Al, Ca or Mg are also not suitable for reducing rutile, as Ti forms a number of very stable solid solutions of oxygen and thus the metal product is highly contaminated with oxygen. The method currently used involves a chlorination process to produce gaseous TiCl4 which has a boiling point of only 137OC. TiO2 (s) + 2 C (s) + 2 Cl2 (g) = TiCl4 (g) + 2 CO (g) GO = -295 kJ

The chloride is reduced by Mg at 850O C in a sealed crucible by the following reaction: TiCl4 (g) + 2 Mg (l) = 2 MgCl2 (l) + Ti (s) Sufficient heat is required only to melt the resulting MgCl2 whose melting point is 714OC so that it separates from the Ti sponge product. Vacuum distillation is used to drive of the MgCl2 and any remaining Mg from Ti sponge by heating above the boiling point of MgCl2 at 1418OC. The Kroll process is a time consuming labour intensive process. After loading Mg ingots into a steel reactor, the reactor is then welded for sealing. The reactor is then heated to the operating temperature and the reactions proceed slowly over several days to form the metallic Ti product. The reactor is then allowed to cool, the weld broken and products removed by hand and segregated by quality as both morphology and composition variations are unavoidably present. Each batch is then subjected to vacuum distillation. Even the largest plant is capable of producing not more than 1 tonne per day and economy of scale is not available. The chlorine and the chlorides in the gaseous form are noxious and serious pollutants requiring considerable care. Thus Ti is currently very expensive severely restricting its potential applications despite having excellent properties in terms of high strength, low density and a good corrosion resistance.

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Case Studies Recycling of Metals Recovery of Metals and Materials Re-use of Wastes from Metal Production Decrease in Energy Consumption and Carbon Emission Sustainability

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PART III - MODULE 3 (M3): EXTRACTION AND RECYCLING DR RV KUMAR QUESTION SHEET 1

1. Calculate the CO/CO2 ratio in equilibrium with carbon at 1000K assuming the total pressure to be 2 atm (202650 N/m2), given the Go values at 1000K for the following reactions: 2 C + O2 2CO C + O2 CO2 -398.7 kJ -393.3 kJ

If the temperature is increased would you expect the ratio to increase, decrease or remain the same? Why? Discuss the role of Coke in the iron blast furnace. In the blast furnace, discuss the thermal, the chemical and the aerodynamic implications of both the direct reduction with C in the Coke and the indirect reduction with CO. 2. Calculate the maximum solubility of oxygen in pure iron at 1873 and 1773 K, given: log K = -6372 / T + 2.73 and eoo = - 0.2 for the reaction: FeO (l) = Fe(l) + O (1 wt % standard state) Decarburisation in steelmaking proceeds through the following reactions: C (1 wt % std state) + O (1 wt % std state) = CO(g) Go = -15466 -43 T (Joules) Assuming the temperature to be 1873K and pressure of CO at 1atm, and ignoring the interaction parameters, plot graphically the increase in oxygen content as carbon in steel decreases from 0.8 to 0.01%. What would be the effect if at the final values of C and O, the molten steel is subject to a vacuum of 0.001 atm? What is the effect of decreasing the temperature to 1823K while retaining the vacuum at 0.001 atm? 3. Using the ionic theory of slags explain why dephosphorisation of liquid iron is feasible in the basic oxygen steelmaking process while it is impossible in the blast furnace. What form will a mixed molecular-ionic theory take to investigate the same reaction?

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4. In the BOF steel making, at the end of refining explain why low carbon steel will result in low Si steel? How can a high Si, but low C steel be produced? A heat of steel contains 0.002 wt% oxygen. Vanadium is to be added in the ladle at 1830K to make steel containing 1 wt% V. To what extent must the oxygen be reduced to prevent the loss of V, which is relatively expensive? Given: 2 V (1 wt % std state) + 3 O (1 wt % std state) = V2O3 (s) Go = -779654 + 267 T (Joules) How is steel deoxidised without simultaneously decarburising? 5. Liquid steel is deoxidised with aluminium by the following reaction: 2 Al (1 wt% standard state) + 3 O (1 wt% standard state) = Al2O3 (s) and the standard free energy change for the above reaction is: Go (J) = -1119,590 + 340 T Assuming that the deoxidation is carried out at 1873K and the deoxidation product is pure Al2O3, calculate the concentration of oxygen in liquid steel for the following concentrations aluminium dissolved in molten steel: (1) 0.001 wt% (2) 0.005 wt% (3) 0.1 wt % and (4) 1.0 wt%. Explain why in practice at aluminium concentration beyond a certain value (typically 0.005 wt%), the soluble oxygen concentration achieves a minimum and then increases sharply. Give reasons why calcium is often added with aluminium in deoxidation practice. 6. Assuming desulphurisation takes place by the following reaction: 4 CaO(s) + Si (1 wt % standard state) + 2 S (1 wt % standard state) = 2 CaS(s) + 2CaO. SiO2 (s) GO (J) = - 450980 + 149 T

in hot metal containing 3 wt % C and 1 wt % Si. Calculate the equilibrium sulphur content at 1773 K, given the following data for the relevant interaction parameters: eSSi = 0.07 eSiSi = 0.11 eSC = 0.11 eSiC = 0.17 eSS = -0.03 eSiS = 0.06

Why is desulphurisation not very effective during the steelmaking stage in the basic oxygen steelmaking process?

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PART III - MODULE 3: EXTRACTION AND RECYCLING DR RV KUMAR Question Sheet 2 1. (a) During decarburisation of liquid steel at a temperature of 1873 and a pressure of one atmosphere, samples were analysed for carbon and oxygen to monitor the progress of the reaction. The following analysis were obtained: wt % C 0.1 0.05 wt % O 0.025 0.048

O C Determine the values for the interaction parameters eC and eO , given the following data: C ( 1 wt % standard state) + O (1 wt % standard state) = CO (g)

For which the equilibrium constant K is expressed as: log10 K = 1056/T + 2.13
C O and the self-interaction parameters eC = 0.3 and eO = 0

(b) Explain why adding a combination of deoxidisers such as Si + Mn, can give lower oxygen content in liquid steel than when the elements are added individually. (Tripos 2007) 2. Consider molten steel at 1873K which contains 0.2 wt % A and 300 ppm (by wt) of N. Calculate the temperature at which AlN will begin to precipitate, given for the reaction: Al (1 wt % standard state) + N (1 wt % standard state) = AlN (s) GO = -267, 483 + 119.52 T
N Al [The interaction parameters at 1873K are: e Al = 0.58; eN = 0.028 ]

Discuss the role of the above reaction with respect to grain refining in steel.

(Tripos 2006)

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3.

(a) Sketch a typical flow sheet for producing copper from a sulphide ore by a pyrometallurgical route. (b) Write down the key chemical and electrochemical reactions involved in the production of aluminium by the Hall-Heroult Cell. (c) Calculate the theoretical standard cell potential of the Hall-Heroult cell at 1273 K from the following thermodynamic data: 4/3 Al (l) + O2 (g) = 2/3 Al2O3 (s) C (s) + O2 (g) = CO2 (g)
Go1273 (kJ) = -840.18 Go1273 (kJ) = -397.1

Explain briefly why the operating cell voltages are more than 5 times higher t than the theoretical standard cell potential. (Tripos 2005) 4. Discuss the following briefly: (a) Deoxidation of molten steel and inclusion control (b) Use of direct reduced iron (DRI) as a substitute for ferrous scrap in electric arc furnace steelmaking (c) Use of molten salt rather than aqueous electrolyte for electrowinning aluminium, sodium, calcium and lithium 5. for Explain the basis on which limiting current density in an electrowinning cell producing Copper can be estimated?

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