Extraction Metallurgy Student

Extraction Metallurgy
Part 2: Case studies
Dr. C.B. Perry ( y (C306) )
http://www.gh.wits.ac.za/chemnotes
Chem 3033
Extraction Metallurgy
Part 2: Case studies
Copper Pyrometallurgy route and environmental concerns The concerns. hydrometallurgical alternative. Hydrometallurgical processes ion exchange processes, solvent extraction, and bacterial leaching. Iron Pyrometallurgy and the blast furnace. Silicon The electric arc furnace. Purification by the Czochralski process. Aluminium Electrolytic reduction. The siderophiles The extraction of Au and the Pt group metals and their purification.
Pyrometallurgy of copper
Reminder: Pyrometallurgy is the use of heat to reduce the mineral to the free metal, and usually involves 4 main steps:
1. 1 Calcination: thermal decomposition of the ore with associated elimination of a volatile product. 2. Roasting: a metallurgical treatment involving gassolids reactions at elevated temperatures. 3. Smelting: a melting p g g process which separates the p chemical reaction products into 2 or more layers. 4. Refining: treatment of a crude metal product to improve its purity.
Cu ore usually associated with sulphide minerals. Most common source of Cu ore is the mineral chalcopyrite (CuFeS2), which accounts for 50% of Cu production. Other important ores include: chalcocite [Cu2S], malachite [CuCO3 Cu(OH)2], azurite [2CuCO3 Cu(OH)2], bornite (3Cu2S Fe2S3), covellite (CuS).
The following steps are involved in Cu extraction: 1. 1 Concentration 2. 2 Roasting 3. 3 Smelting 4. 4 Conversion 5. 5 Refining
1. Concentration
Only ~0 7% of the extracted ore contains Cu 0.7% Finely crushed ore concentrated by the froth-flotation process: Copper ore slurry mixed with: Lime water to give basic pH Pine oil to make bubbles An alcohol to strengthen bubbles A chemical collector
1. Concentration (cont.)
Chemical collectors such as xanthates ( (salts & esters of xanthic acid), ), dithiophosphates, or thionocarbamates make the ore surface hydrophobic. y p
Hydrophobic attracted H d h bi tt t d to hydrocarbon pine oil
CH3 H3C O
S X S O R
Na3PS2O 2 S R1 O N R2 H
Hydrophilic attracted H d hili tt t d to sulphide minerals

S S K
Potassium amyl xanthate
Raising the pH causes the polar ends to ionize more more, thereby preferentially sticking to chalcopyrite (CuFeS2) and leaving pyrite (FeSs) alone. Air is bubbled through the suspension. g p Finely divided hydrophobic ore particles latch on to the air b bbl and t i bubbles d travel t th surface where a f th i l to the f h froth is formed. The froth containing the Cu ore is skimmed off and reprocessed. reprocessed
In this manner, the ore is manner concentrated to an eventual value of over 28% Cu. The remaining material ( g (sand particles & other impurities) sink to the bottom & is discarded or reprocessed t extract other d to t t th elements.
Froth-flotation
2. Roasting
Involves partial oxidation of the sulphide mineral with air at between 500C and 700C. For chalcopyrite, the main reactions are:
CuFeS2(s) + 4O2(g) CuSO4(s) + FeSO4(s) 4CuFeS2(s) + 13O2(g) 4CuO(s) + 2Fe2O3(s) + 8SO2(g) exothermic, Reactions are exothermic roasting is an autogenous process requiring little or no additional fuel. NB not all th sulphides are oxidised, only around 1/3 NB, t ll the l hid idi d l d 1/3. Rest remain as sulphide minerals. The gases produced contain around 5 15% SO2, which is used for sulphuric acid production.
2. Roasting (cont.)
Objectives of roasting: 1) 2) 3) Remove part of the sulphur. Convert iron sulphides into iron oxide and iron sulphate to facilitate removal during smelting. To pre-heat the concentrate to reduce amount of energy needed by the smelter smelter.
3. Smelting
Smelting consists of melting the roasted concentrate to form 2 molten phases:
1) a sulphide matte, which contains the iron copper matte iron-copper sulphide mixture. 2) an oxide slag which is insoluble in the matte and slag, matte, contains iron oxides, silicates, and other impurities. Smelting is carried out at around 1200C, usually with a silica flux to make the slag more fluid. The matte layer sinks to the bottom, and the slag layer floats on top of the matte & is tapped off & disposed of.
3. Smelting (cont.)
The main reaction is the reduction of copper oxides (formed during roasting) back into copper sulphide to ensure that they migrate into the matte phase: FeS(l) + 6CuO(l) 3Cu2O(l) + FeO(l) + SO2(g) FeS(l) + Cu2O(l) FeO(l) + Cu2S(l) Cu2S(l) + FeS(l) Cu2SFeS(l) (matte)
4. Conversion
After smelting, matte contains from between 30 to smelting 80% Cu in the form of copper sulphide. The sulphur is removed by selective oxidation of the matte with O2 to produce SO2 from S but leave Cu S, metal. Converting is carried out in two stages: 1) an iron removal stage and 2) a copper making stage stage, copper-making stage.
4. Conversion (cont.)
Iron removal
A silica flux is added to keep the slag (see below) molten. lt Air is blown into the converter to oxidize the iron sulphide according to the following reaction:
2Cu2S FeS(l) + 3O2(g) + SiO2(l) 2FeOSiO2(l) + 2SO2(g) + Cu2S(l) SFeS(l) 2FeO SiO
Si added to help form FeO slag. The oxidized Fe and Si form a slag (insoluble in matte) that is skimmed off & disposed off.
4. Conversion (cont.)
Copper making
The sulphur in the Cu2S can now be oxidized to leave behind metallic copper according to the following reaction: Cu2S(l) + O2(g) 2Cu(l) + SO2(g) The d Th end product i around d t is d 98.5% pure & is known as blister bli t copper b because of f the broken surface created by th escape of t d b the f SO2 gas.
5. Refining
Almost all copper is refined by electrolysis electrolysis. The anodes (cast from blister copper) are placed into an aqueous CuSO4/H2SO4 solution. Thin sheets of highly pure Cu serve as the cathodes. Application of a suitable voltage causes oxidation of Cu metal at the anode anode. Cu2+ ions migrate through the electrolyte to the cathode, where Cu metal plates out.
5. Refining (cont.)
Metallic impurities more active then Cu are oxidized at the anode, but dont plate out at the cathode. p Less active metals are not oxidized at the anode, but collect at the bottom of the cell as a sludge sludge. The redox reactions are:
Cu(s) Cu2+(aq) + 2e2 Cu2+(aq) + 2e- Cu(s) Ered = -0.83V 0 83V
5. Refining (cont.)
Environmental impact
Large amount of gases produced present air pollution p problems, in p particular SO2 gas acid rain. g Dust produced contains heavy metals such as p y mercury, lead, cadmium, zinc health problems. Waste water contaminated with:
Insoluble substances, mostly waste sludge (finely ground rock). Soluble substances (heavy metals, sulphates). Chemicals from flotation process.
Environmental impact
Typical Air Emissions
Typical Liquid Effluents T i l Li id Effl t
Hydrometallurgy of copper
Advantages
Much more environmentally friendly than pyrometallurgy. Compared to pyrometallurgy, only a fraction of the pyrometallurgy gases liberated into the atmosphere. Emissions of solid particles comparatively nonexistent.
Disadvantages
L Large amount of water used, greater potential for t f t d t t ti l f contamination. Waste waters contain soluble metal compounds, chelating compounds & organic solvents.
The following steps are involved: 1. 1 Ore preparation 2. 2 Leaching 3. 3 Solution purification 4. 4 Metal recovery
1. Ore preparation
Ore undergoes some degree of comminution (crushing & pulverisation) to expose the Cu oxides & sulphides to leaching solution.
1. Ore preparation (cont.)
Amount of comminution depends on quality of ore:
Higher grade ore more comminution. Lower grade ore less comminution. (Why??)
If possible, ore is pre-concentrated; reject ore that contains very little Cu.
2. Leaching
Definition : The dissolution of a mineral in a solvent, while , leaving the gangue (rock or mineral matter of no value) behind as undissolved solids.
C i normally l Cu is ll leached b one of th h d by f three methods: th d

(a) Dump leaching (b) Heap leaching (c) Bacterial leaching
2. Leaching (cont.) (a) Dump leaching
Leaching solution trickled over a dump. Runoff solution collected & th C recovered f R ff l ti ll t d the Cu d from it it. A slow process that takes months or years to complete. Typically only around 60% of the Cu in the dump is recovered.
2. Leaching (cont.) (b) Heap leaching
Similar to dump leaching except ore not simply dumped on a hillside, but is hill id b t i crushed t gravel size & piled onto an artificial h d to l i il d t tifi i l pad. After leaching (6 months to 1 year) gangue is removed from pad, disposed of & replaced with fresh ore.
2. Leaching (cont.)
Leaching reactions
Nature of ore determines if leaching is non-oxidative or oxidative. Non oxidative Non-oxidative leaching: No change in oxidation state. e.g. (1) dissolution of copper sulphate by water:
2+ 2CuSO4(s) + H2O(l) Cu2 (aq) + SO42 (aq)
(2) dissolution of alkaline materials by acid:

Cu2(OH)2CO3(s) + 2H2SO4(aq) 2CuSO4(aq) + CO2(g) + 3H2O(l)
2. Leaching (cont.)
Oxidative leaching: Many ores only soluble once oxidised oxidised. e.g. covellite (CuS) much more soluble if oxidised to CuSO4 CuS(s) + O2(g) CuSO4(aq) CLASS EXERCISE : work out which species is oxidised, and which is reduced, and write out the balanced half reactions for reduced each.
2. Leaching (cont.) (c) Bacterial leaching
Several bacteria, especially Thiobacilli are able to bacteria Thiobacilli, solubilise metal minerals by oxidising ferrous to ferric iron, iron as well as elemental sulphur sulphide and other sulphur, sulphide, sulphur compounds to sulphate or sulphuric acid. 20 to 25% of copper produced in the USA, and 5% of the worlds copper is obtained by bacterial leaching leaching. Very slow process; takes years for good recovery But low investment and operating costs costs.
Thiobacilli
A acidotolerant; some grow at pHs as l Are id t l t t H low as 0 5 0.5 A t l Are tolerant against heavy metal t i it t i th t l toxicity. A chemolithoautotrophs (C source i CO2 & energy Are h lith t t h is derived from chemical transformation of inorganic matter). matter)
Mechanisms
Generalised reaction : M(II)S + 2O2 M2+ + SO42 Two mechanisms: (a) indirect mechanism involving the ferric-ferrous cycle, and (b) di t mechanism th f i f l d direct h i involving physical contact of the organism with the sulphide mineral. l hid i l
Mechanisms: Indirect
First step: ferrous sulphate is converted into ferric sulphate by the action of Acidithiobacillus ferrooxidans: 4FeSO4 + O2 + 2H2SO4 2Fe2(SO4)3 + 2H2O
CLASS EXERCISE : work out which is ferric and which is ferricferrous sulphate, and write out the balanced half reactions for each.
Ferric sulphate is a strong oxidising agent capable of dissolving a range of sulphide minerals minerals. In the case of chalcopyrite: CuFeS2 + 2Fe2(SO4)3 CuSO4 + 5FeSO4 + 2S
The elemental S produced by the indirect method can be b converted t H2SO4 b A idithi b ill t d to by Acidithiobacillus ferrooxidans:
The H2SO4 helps maintain the pH at levels f favourable for bacterial growth.
Mechanisms: Direct
Bacteria actually adheres to the mineral surface prior to t enzymatic attack. ti tt k Th mineral is oxidised with oxygen t sulphate and The i li idi d ith to l h t d metal cations without any detectable intermediate occurring. i I the case of covellite: In th f llit CuS + 2O2 CuSO4
Compared to other extraction techniques:
Traditional methods expensive (i.e. roasting + smelting) & require hi h concentrations of C i ore. lti ) i high t ti f Cu in B t i can effectively deal with l Bacteria ff ti l d l ith low [C ] as th [Cu] they simply ignore surrounding waste materials. Up to 90% extraction efficiency.
Compared to other extraction techniques:
ADVANTAGES: Economical: Simpler, cheaper, less infrastructure. More environmentally friendly; no SO2 emissions, less landscape damage. DISADVANTAGES: Economical: Very slow compared to smelting; less profit. profit Delay in cash flow for new plants plants. Environmental; Toxic chemicals sometimes produced. H2SO4 pollution Precipitation of heavy ions (Fe Zn, pollution. (Fe, Zn As) pollution.
3. Solution Purification
Leaching reactions not perfectly selective other elements in solution as well, not just Cu. These need to be removed removed. After leaching, Cu in solution can be very dilute leaching dilute. need a way to concentrate it. Both of these are generally done using ion exchange processes, processes the two most common being ion exchange chromatography, and solvent extraction.
Ion exchange chromatography DEFINITION: a solution containing a mixture of metal ions i contacted with a resin th t i i i is t t d ith i that is insoluble i th l bl in the metal-ion solution. Ion-exchange resin consists of an inert solid phase to which labile functional groups are chemically bonded. Functional groups can either be acidic (H+) or basic (OH) groups th t exchange with cations (M+) or that h ith ti anions (M), respectively. The ion-exchange process is reversible.
Ion exchange chromatography: Theory Analyte molecules retained on a column (stationary phase) b h ) based on coulombic (i i ) i t d l bi (ionic) interactions. ti St ti Stationary phase has ionic functional groups (R-X) h h i i f ti l (R X) that interact with analyte ions of opposite charge. Two types: cation exchange chromatography: R-X R X-C+ + M+B- R X-M+ + C+ BR-X anion exchange chromatography: i h h t h R-X+A- + M+B- R-X+M- + M+ A-
Cu Ion exchange chromatography
C b Carboxyl groups exchanges the i i currently h ld l h h ion it l holds (H+) for a Cu2+ ion. Th C 2 i l t released b contacting it with a The Cu2+ is later l d by t ti ith stripping solution (very high H+ conc.).
3. Solution Purification: Solvent extraction
DEFINITION: a method to separate compounds based on th i relative solubilities i 2 diff b d their l ti l biliti in different t immiscible liquids. In industry, this is usually set up as a continuous process
Organic + aqueous stream pumped into a mixer. Organic (containing an extractant) and aqueous components mix, and i t t i d ion transfer occurs between them. f b t th Once ion transfer is complete (equilibrium), mixture is allowed to separate separate. Aqueous solution is removed & the organic phase (containing the Cu2+) is mixed with an aqueous stripping solution. Cu2+ moves back into the aqueous p q phase, and the two , phases are again allowed to separate. The aqueous phase (containing the Cu2+) is removed & the organic phase is recycled back into the first mixer.
Extractants The most successful extractants for copper are of the orthohydroxyoxime type:
OH R R
1
OH
R = alkyl ,phenyl, or H phenyl R1 = alkyl
F Function b means of a pH-dependent cation-exchange i by f Hd d i h mechanism: Cu2+ + 2HA CuA2 + 2H+ (where H in HA denotes the replaceable, phenolic proton)
Extractants At low pH (1.5 2.0) the ortho-hydroxyoxime extractant complexes the Cu Cu. back extraction During back-extraction (stripping stage) the pH is lowered further, releasing the Cu, and regenerating the hydroxyoxime for recycle to the extraction stage. y g Aqueous feeds (leach solution) typically contain more iron per litre than copper. For commercial success, the extractant must have a greater selectivity for Cu than Fe.
Extractants Cu2+ forms square-planar complexes with hydroxyoxime: R 1 N O R Cu 1 N O R R O H H-bonding between the oximic H and the phenolic O affords this 2:1 complex unusual stability. The formation constant (K2) for the 2:1 complex is much ( greater than for the 1:1 complex.
O H O H
Extractants The tris(salicylaldoximato)iron(III) complex is octahedral, and no extended planar ring structure is possible between the 3 oxime ligands.
stability of Fe(III) complex is less than Cu(II) complex, which allows the extraction of Cu to be carried out at lower pH than what is required for efficient Fe extraction.
4. Metal Recovery:
At this point, the metal needs to be recovered from solution i th solid f l ti in the lid form. Thi is either achieved chemically, or This i ith hi d h i ll electrochemically.
4. Metal Recovery:
Chemical recovery
Dissolved copper will plate out on an iron surface according to the following reaction: g g Cu2+(aq) + Fe(s) Fe2+(aq) + Cu(s) Why?? Reduction half-reactions: Cu2+(aq) + 2e Cu(s) 2 Fe2+(aq) + 2e Fe(s) Ered = +0.34 V Ered = -0.44 V 0 44
Ered for the Cu2+ half-reaction is more positive than for 2+ the Fe2 half reaction which leads to Cu being reduced and Fe oxidised.
4. Metal Recovery:
Chemical recovery
Solutions containing dissolved copper are thus run through a bed of shredded scrap iron, resulting in the g p g copper ions being plated out as solid Cu on the iron surface. For the process to be efficient, the surface of the p scrap iron must be large.
4. Metal Recovery:
Electrowinning
Electrochemical recovery
An electrochemical process for precipitating metals from solution. f l ti
4. Metal Recovery:
Electrowinning
A current is passed from an inert anode through a liquid leach solution containing the metal so that the metal is extracted as it is deposited onto the cathode cathode. The anode is made out of a material that will not easily oxidise or dissolve, such as lead or titanium.
4. Metal Recovery:
Electrorefining
The anodes consist of unrefined impure metal. Current passes through the acidic electrolyte corroding the anode into the solution. Refined pure metal deposited onto the cathodes. Metals with a greater Ered than Cu (such as Zn and Fe) remain in solution. Metals with a lower Ered than Cu (Au, Ag) accumulate as an anode sludge collected & sold f f th d l d ll t d ld for further refining.
4. Metal Recovery:
Electrorefining
Summary:
Silicon production
Ellingham di Elli h diagrams
Follow the 2nd law of thermodynamics: th d i G = H - TS Plot G vs T (y = m X + c)
rG /kJ mol-1 J
Temperature /C
Ellingham diagrams
Lower the position of a metal in the Ellingham diagram = greater stability of its oxide. A metal found in the Ellingham diagram can act as a reducing agent for a metallic oxide found above it it. Stability of metallic oxides decrease with increase in temperature. Intersection of two lines imply the equilibrium of oxidation and reduction reaction between two substances. Reduction possible at the intersection point and higher temperatures where the G p g p line of the reductant is lower on diagram than the metallic oxide.
Silicon production
More difficult to extract Si than either Cu or Fe.
rG /kJ mol-1 G m
Temperature /C
Silicon production
Silicon of between 96 to 99% purity is achieved by reduction of quartzite or sand (SiO2, also called silica) High temperatures required achieved in an electric arc furnace. Reduction carried out in the presence of excess silica to prevent accumulation of silicon carbide (SiC) : 2SiO2(l) + 3C(s) Si(l) + 2CO2(g) + SiC(s) 2SiC(s) + SiO2(l) 3Si(l) + 2CO(g)
Silicon production
The electric arc furnace
Silica and carbon fed in through the top, liquid Si collected at the bottom. Temps of 2000K y achieved by an electric arc burning between graphite electrodes. An arc forms between the charge and the electrodes. Th charge is heated both b current passing th The h i h t d b th by t i through th charge and h the h d by the radiant energy evolved by the arc.
Silicon production
The electric arc furnace
Electric arc furnaces require huge amounts of electricity. A midsized furnace would have a transformer rated about 60,000,000 volt-amperes with a secondary voltage between 400 and 900 volts and a secondary current in excess of 44,000 amperes.
Silicon production
Applications
Si is the 2nd most abundant element in the earths crust (~28%). Principal constituent of natural stone glass concrete stone, glass, & cement. Largest application of pure Si (metallurgical grade) is in the manufacture of Al-Si alloys to produce cast parts (for automotive industry). Important constituent of electrical steel (modifies the resistivity & ferromagnetic properties). Added to molten cast iron to improve its performance in casting thin sections.
Silicon production
Applications
2nd largest application is in the production of silicones. These are polymers containing Si-O and Si-C bonds. Typically heat-resistant, nonstick, and rubberlike, they are frequently used in cookware, medical applications, sealants, lubricants, and insulation. Electronics industry ultra-pure silicon wafers used in electronic components such as transistors, solar cells, integrated circuits, microprocessors & various semiconductor devices.
Silicon production
Purification
Ultra-pure silicon is required for the production of semiconductors. i d t
Silicon production
Purification
Semiconductor-grade Si produced by converting crude Si to more volatile compounds like SiCl4. These are then purified by exhaustive fractional distillation. Reduced back to Si with pure H2. Finally the high-purity Si is melted and large single Finally, high purity crystals are grown by the Czochralski process. Electronic grade Si is required to be 99.999999999% pure!
Silicon production
Purification: Th Czochralski process P ifi ti The C h l ki
Ultra pure Si (only a few ppm of impurities) is melted in a crucible Ultra-pure crucible. Dopant impurities (B or P) can be added to make n-type or p-type silicon (influences the electrical conductivity). A seed crystal mounted on a rod is dipped into the molten Si. Seed crystal rod pulled up & rotated at the same time. By carefully controlling the temp gradients rate of pulling and gradients, pulling, rotation speed, a large single-crystal (called a boule) can be extracted from the melt.
Silicon production
Silicon production
The boule is then ground down to a standard diameter and sliced into wafers much like a wafers, salami. The wafers are etched and polished, and move on to the process line. A point to note however, is that due to "kerf" losses (the width kerf of the saw blade) as well as polishing losses, more than half of the carefully grown, very pure, single crystal silicon is thrown away before the circuit fabrication process even begins!
Silicon production
Electrochemical El t h i l preparation: ti
A new method that uses electrolysis to reduce SiO2 to elemental Si. Advantageous because it avoids the high energy costs associated with the older carbothermic route, and also , reduces the CO2 emissions considerably. SiO2 is usually an insulator, and doesnt conduct electricity, but it has been shown that a tungsten wire sealed within a quartz tube with the tungsten end exposed, can act as a exposed cathode.
Silicon production
The anode is usually graphite, and the reduction is carried graphite out in a solution of molten CaCl2 at around 850 C. a) SEM of W-SiO2 electrode before reduction. b) After reduction. ) f c) After washing. d) Side view view.
Silicon production
Conversion of quartz to Si occurs at the three-phase three phase boundary between the SiO2, the electrolyte, and the flattened end of the tungsten wire. g This provides enough impetus for the electrochemistry to kick in properly as the silica is gradually converted to conducting silicon. This reaction should theoretically propagate through the silica electrode, but in reality it grinds to a halt very quickly electrode quickly. y Reason for this is that the molten electrolyte cannot penetrate through the newly formed Si layer on the surface. three-phase boundary formation halted.
Silicon production
Solution: replace solid quartz electrode with SiO2 powder pressed into pellets & sintered. Resulting electrode porous enough to allow electrolyte to penetrate deeply into the material.
a) SEM of SiO2 powder b) reduced Si powder.
Silicon production
Aluminium production
Most abundant metallic element in the earths crust. But, extremely rare in its free form. Once considered as a precious metal more valuable than gold! g Al is a highly reactive metal that forms strong bonds g y g with O. Requires a large amount of energy to extract from Al2O3.
Cannot be reduced directly by carbon since Al is a stronger reducing agent than C. g g g Must therefore be extracted by electrolysis. Aluminium production involves two steps: 1) purifying Al2O3 from bauxite (the Bayer process) and 2) ( y p ) ) converting Al2O3 to metallic Al (The Hall-Heroult process). ) Primary Al ore is bauxite, which consists of: Gibbsite - Al(OH)3 (most extractable form) Boehmite - AlOOH (less extractable than Gibbsite) Diaspore - AlOOH (difficult to extract)
The B Th Bayer process: Step 1: Dissolution
The hydrated aluminium oxides are first selecti el h drated al mini m o ides selectively dissolved from bauxite: Al(OH)3 + NaOH NaAlO2 + 2H2O (Gibbsite dissolution) AlOOH + NaOH NaAlO2 + H2O (Boehmite dissolution) An undesirable side reaction is the formation of red mud mud, which occurs when Al(OH)3 reacts with dissolved Kaolinite clay:
5Al2Si2O5(OH)4 + 2Al(OH)3 + 12NaOH 2Na6Al6Si5O17(OH)10 + 10H2O
Red mud formation consumes dissolved Al and represents a Al loss.
The B Th Bayer process: Step 2: Solid-Liquid Separation
The digested bauxite now consists of 1 liquid and 2 solid components:
Caustic liquid soln with dissolved Al soln. Al. Undissolved coarse material (sand). Precipitated fines (red mud).
Sand (mainly undissolved silicates) easily removed since they settle very rapidly rapidly. The red mud is removed by adding a flocculent to increase the settling rate. The Al content of the red mud is recovered & forms part of the liquid layer.
The B Th Bayer process: Step 3: Precipitation
The remaining solution is supersaturated containing supersaturated, around 100-175 grams of dissolved Al2O3 per litre. Al(OH)3 is precipitated out by adding seed crystals since Al(OH)3 doesnt crystallise out easily on its own doesn t own. size, Once the crystals have reached the desired size they are removed, washed, and filtered. The spent liquor is reheated, recausticised and recycled. recycled
The B Th Bayer process: Step 4: Calcination
Wet crystals of Al(OH)3, obtained from the precipitation step are dried by heating to around 1300 1500 C C. This process also converts the Al(OH)3 to Al2O3: 2Al(OH)3 Al2O3 + 3H2O
The B Th Bayer process: Problems
Problems result from the coordination chemistry of Al in basic solutions. Generally accepted structures:
Leads to extensive H-bonding between aluminate ion & solvent, which in turn leads to high viscosity of these solvent solutions. In turn leads to problems with materials handling & heat exchange.
The B Th Bayer process: Problems
In addition, the inertness of Al(III) leads to slow rates addition of crystallisation, requiring large vessels & large volumes of circulating solution & seed material material.
The H ll H Th Hall-Heroult process: lt
Reactive metals (e g Mg and Na) can be produced by (e.g. electrolysing a molten chloride salt of the metal. Not the case for AlCl3 since it sublimes rather than melts. Even under sufficient pressure, molten AlCl3 is an electrical insulator & cannot be used as an electrolyte electrolyte. Would have to be dissolved in a conductive salt (NaCl or KCl) KCl). Commercially viable production of Al only commenced once the use of cryolite (Na3AlF6) was discovered.
Cryolite is electrically conductive and dissolves Al2O3. conductive,
Anhydrous Al2O3 melts at over 2000C which is too 2000 C high to be used as a molten medium for electrolytic reduction of Al Al. Al2O3 dissolved in cryolite has a m p of 1012C & is a m.p. 1012 C good electrical conductor. Graphite rods are used as anodes & are consumed in the electrolytic process process. vessel graphite. The cathode is a steel vessel, lined with graphite
The electrode reactions are as follows: Anode: C(s) + 2O2-(l) CO2(g) + 4eCathode: 3 - + Al3+(l) Al(l) C th d 3e
CLASS EXERCISE : Write out the balanced overall reaction
CLASS EXERCISE : Calculate the mass of Al that will be p produced in 1.00 hr by the electrolysis of molten Al2O3 , using a y y g current of 10.0 A. F (Faraday constant) = magnitude of electric charge per mole of electrons = 96500 C mol-1.
Step 1: calculate the number of coulombs (C) from the current (I) and the time (t):
Step 2: find the number of moles of electrons:
Step 3: find the mass of Al produced:
Electrolytic reduction of Al is costly (3 e- required for every atom of metallic Al reduced). The electrical voltage used is only around 5.25 V, but the current required is very high typically 100 000 to high, 100,000 150,000 A or more! Electrical power is the single largest cost in Al production, production Al smelters are typically located in areas with inexpensive electric power, like S.A.
Pyrometallurgy of iron
Still the most important pyrometallurgical process economically. The most important sources of iron are hematite (Fe2O3) and magnetite (Fe3O4). Prehistorically, iron was prepared by simply heating it with charcoal in a fired clay pot. Today, the reduction of iron oxides to the metal is accomplished in a blast furnace. furnace
Blast furnace:
1) Hot gas blast ) g 2) Melting zone 3) Reduction of FeO 4) R d ti of F 2O3 Reduction f Fe 5) Pre-heating zone 6) Feed of ore ore, limestone + coke 7) Exhaust gases ) g 8) Column of ore, coke + limestone 9) R Removal of slag l f l 10) Tapping of molten pig iron 11) W t gas collection Waste ll ti
The iron ore, limestone, and coke are added to the top of the furnace. Coke is coal that has been heated in an inert atmosphere to drive off volatile components (~ 80 90% C). Coke is the fuel, producing heat in the lower part of the furnace. Is also the source of the reducing gases CO & H2. Limestone (CaCO3) serves as the source of CaO which reacts with silicates & other impurities in the ore to form slag. slag
Slag:
Most rocks are composed of silica (SiO2) and silicates (SiO32-) & are almost always present in the ore. These compounds dont melt at the furnace temperature & would eventually clog it up. An important chemical method to remove these is by use of a flux which combines with the silica & silicates to produce a slag. Slag collects at bottom of furnace & doesnt dissolve in the molten metal.
Slag:
The heat of the furnace decomposes the limestone to give calcium oxide (e.g. of a calcination reaction). CaO (a basic oxide) reacts with silicon dioxide to give calcium silicate.
CaCO3(s) CaO(s) + CO2(g)
CaO(s) + SiO2(s) CaSiO3(l) Slag helps protect the molten iron from re-oxidation. Sl is used in road making, and can also b Slag i di d ki d l be combined with cement.
Air is blown into the bottom of the furnace, and combusts with the coke to raise the furnace temp up to 2000C : 2C(s) + O2(g) 2CO(g) H H = -221 kJ 221
H2O in the air also reacts with the coke: C(s) + H2O(g) CO(g) + H2(g) H = +131 kJ
Since this reaction is endothermic, if the blast furnace gets too hot water vapor is added to cool it down hot, without interrupting the chemistry.
Molten iron is produced lower down the furnace & removed. Slag is less dense than iron & g can be drained away. The iron formed (called pig iron) still contains around 4-5% C, 0.61.2% Si, 0.4-2.0% Mn + S and P and needs to be further processed.
At around 250C (top of the furnace), limestone is calcinated: CaCO3(s) CaO(s) + CO2(g) Al at the top of the furnace, hematite is reduced: Also t th t f th f h tit i d d 3Fe2O3(s) + CO(g) 2Fe3O4(s) + CO2(g) Reduction of Fe3O4 occurs further down the furnace (~700C): ( 700C): Fe3O4(s) + CO(g) 3FeO(s) + CO2(g) Near the middle of the furnace (1000C) Fe is produced: FeO(s) + CO(g) Fe(s) + CO2(g)
Cast iron
Cast iron is made by remelting pig iron & removing impurities such as phosphorous and sulphur. The viscosity of cast iron is very low, & it doesnt shrink much when it solidifies. ideal for making castings. BUT, it is very impure, containing up to 4% carbon. This makes it very hard, but also very brittle. Shatters rather than deforms when struck hard. These days cast iron is quite rare, often being replaced by other materials.
Steelmaking
Pig iron is brittle, and not directly very useful as a brittle material. Typically, pig iron is drained directly from the blast furnace (referred to as hot metal), and transported to a steelmaking plant while still hot. The impurities are removed by oxidation in a vessel called a converter. The oxidising agent is pure O2 or O2 mixed with Ar. Air can t be used as N2 reacts with iron to form iron cant nitride which is brittle.
Steelmaking
O2 blown directly into molten metal. Reacts exothermically with C, C Si + other impurities impurities. C & S expelled as CO and SO2 gas gas. Si oxidised to SiO2 & incorporates into the slag layer. Iron converter Once oxidation complete, contents poured out & various alloying elements added to produce steels.
Types of iron & steel
Wrought iron iron with all the C removed Soft & removed. easily worked with little structural strength. No longer produced commercially commercially. Mild steel iron containing around 0 25% C Stronger 0.25% C. & harder than pure iron. Has many uses including nails, wire, nails wire car bodies girders & bridges etc bodies, bridges, etc. 1.5% C. High carbon steel contains around 1 5% C Very hard, but brittle. Used for things like cutting tools, and masonry nails nails.
Types of iron & steel
Stainless steel iron mixed with chromium and nickel nickel. Resistant to corrosion. Uses include cutlery, cooking utensils, utensils kitchen sinks etc sinks, etc. Titanium steel iron mixed with titanium Withstands titanium. high temperatures. Uses include gas turbines, spacecraft parts etc parts, etc. manganese. Manganese steel iron mixed with manganese Very hard. Uses include rock-breaking machinery, military helmets, etc. helmets etc
The thermite reaction
Aluminium metal can reduce Iron(III) oxide (Fe2O3) in a highly exothermic reaction. Molten iron is produced at around 3000C. Reaction used for thermite welding, often used to join railway tracks. Fe2O3(s) + 2Al(s) 2Fe(s) + Al2O3(s)
Fe2O3(s) + 2Al(s) 2Fe(l) + Al2O3(s)
CLASS EXERCISE : calculate the thermal energy that is released i the reaction. l d in h i
Component Fe2O3(s) Al(s) Al2O3(s) Fe(s) Hfo (kJ/mol) -822.2 0 -1,669.8 1 669 8 0
Electrowinning of iron
The Pyror process:
Studies into iron extraction by electrowinning from sulphate solutions were first carried out around 50 years ago then subsequently forgotten ago, forgotten. May become important again in the future as new new, more environmentally friendly methods are sought for steelmaking. steelmaking
The Pyror process:
First step is to convert iron pyrite (FeS2) into an acid soluble form (FeS). Achieved by either calcining at 800 to 900 C to expel a loosely bound S or by loosely-bound S, smelting in an electric furnace. Step 2 is a leaching step using H2SO4 to extract iron from FeS: FeS(s) + H2SO4(l) FeSO4(l) + H2S(g) Step 3: before entering the electrowinning cells, the solution is purged with air to remove any remaining H2S.
The Pyror process:
Step 4: Electrolysis Iron is reduced and deposited on Electrolysis. the cathode, while O2 is evolved, and H2SO4 is regenerated at the anode More specifically: anode. At the cathode: Fe2+ + 2e- Fe(s) 2H+ + 2e- H2(g) Fe3+ + e- Fe2+ At the anode: SO42- + H2O H2SO4 + 1/2O2 + 2eFe2+ Fe3+ + e-
The Pyror process:
The Pyror process:
The process was shown to be quite efficient. During a 2 year pilot-plant project, a quantity of iron close to 150 tonnes was produced.
Electrolysis was run for several weeks before stripping was performed, resulting in deposits of performed 13mm or more in thickness.
The Pyror process:
Gold extraction
Gold i i G ld mining
Historical:
Panning sand and gravel containing gold is shaken around with water in a pan. Gold is much pan denser than rock, so quickly settles to the bottom of the pan pan.
Gold extraction
Historical:
Sluicing water is channelled to flow through a sluice-box. Slucebox is essentially a man-made channel with riffles (barriers) at the bottom. bottom Riffles create dead-zones in the water current which allows gold to drop out of suspension suspension. Sluicing and panning results in the direct recovery of small gold nuggets and flakes.
Gold extraction
Modern methods:
Hard rock mining used to extract gold encased in rock. rock Either open pit mining or underground mining. mining
Worlds deepest mine near Carletonville 3778 m below ground & 1949 m b l b l d below sea l level! l!
Gold extraction
Gold G ld ore processing i
Gold cyanidation:
The most commonly used process for gold extraction extraction. Used to extract gold from low-grade ore ore. Gold is oxidised to a water-soluble aurocyanide metallic complex. In this dissolution process, the milled ore is agitated with dilute alkaline cyanide solution and air is solution, introduced (Elsener equation):
4Au(s) 8NaCN(l) 4A ( ) + 8N CN(l) + O2( ) + 2H2O(l) 4N A (CN)2(l) + 4N OH(l) (g) 4NaAu(CN) 4NaOH(l)
Gold extraction
Agitated leaching
Gold cyanidation:
At a slurry concentration of around 50% solids the solids, slurry passes through a series of agitated mixing tanks with a residence time of 20 - 40 hrs hrs. The gold-bearing liquid is then separated from the leached solids in thickener tanks or vacuum filters & the tailings are washed to remove Au and CN- prior to disposal.
Gold extraction
Gold cyanidation:
The aurocyanide complex has an exceptionally high stability constant, 2 [Au(CN)2]- = 2 1038. This high stability constant means that dissolution can be achieved even in the presence of considerable amounts of other metals (Cu, Zn, and Ni). At this point, the dissolved Au needs to be recovered from the cyanide solution Two methods commonly solution. used to achieve this are 1) the Carbon in pulp process, process and 2) the Merrill-Crowe process Merrill Crowe process.
Gold extraction
Heap leaching
Gold cyanidation:
Is an alternative to the agitated leaching p g g process. Drastically reduced gold recovery costs of low grade ore. ore Ore grades as low as 0.3 g p ton can be g per economically processed by heap leaching.
Gold extraction
Heap leaching
Gold cyanidation:
Crushed ore placed in a pile on an impervious barrier. CN- solution allowed t percolate th l ti ll d to l t through th crushed h the h d ore & leaches out the Au. Gold-laden pregnant solution drains out the bottom. y p pp Gold recovered by either Carbon in pulp process or Merrill-Crowe process.
Gold extraction
Heap leaching
Gold cyanidation:
Generally requires 60 to 90 days for processing ore that could be leached in 24 hrs in a conventional agitated leach process. Au recovery is around 70% as compared with 90% in an agitated leach p g plant. BUT, has gained wide favour due to vastly reduced processing costs costs. Frequently, mines will use agitated leaching for high-grade ore & heap leaching for marginal grade ores that would otherwise be considered waste rock.
Gold extraction
Gold recovery:
1) Carbon in pulp overview:
Dissolved aurocyanide is mixed with free activated carbon particles in solution and agitated in leach tanks tanks. The carbon particles are much larger than the ground ore particles. C, Gold has a natural affinity for C and the aurocyanide complex is adsorbed onto the C. Th coarse C particles with b The ti l ith bound [A (CN)2]- are th d [Au(CN) then removed by screening using a wire mesh. Finely ground ore passes th through th mesh. h the h
Gold extraction
1) Carbon in pulp details:
Gold recovery:
On completion of cyanidation, p g p y pregnant p p is pulp transferred to Carbon In Pulp (CIP) process. Pregnant pulp passed through a number of tanks (6 to 8) in series. Tanks are mechanically stirred. Granulated carbon is pumped counter-current to the pulp through the tanks. In the final tank, fresh, or barren carbon comes into contact with low-grade or tailings solution. low grade
Gold extraction
1) Carbon in pulp details:
Gold recovery:
In this tank, the barren carbon has a high activity, and can remove trace amounts of Au < 0.01 mg / L. As the carbon passes through the tanks, it collects increasing quantities of Au from the solution. This is termed loading. T i ll concentrations as hi h as 4000 t 8000 g A / Typically, t ti high to Au ton of C can be achieved on the final loaded C. This represents a gold reco er of 90 99% recovery 90-99%.
Gold extraction
1) Carbon in pulp
Gold recovery:
The loaded carbon is then washed with dil. HCl to remove CaCO3 that precipitates on the C C. Acid washed C then separated from the pulp in the final tank & transferred to the elution circuit. Barren pulp is dewatered ( recycle water & remove p p (to y cyanide for reuse in the process). In the elution circuit the loaded carbon is treated with a circuit, hot cyanide & caustic solution to remove the Au. Reversal of adsorption process Produces a small vol of process. vol. soln. With a high Au conc.
Gold extraction
1) Carbon in pulp
Gold recovery:
The barren carbon is reactivated & recycled for use in the process. process The cyanide & caustic solution containing the Au is either transferred to an electrowinning circuit or Au is plated out onto steel wool wool. The Au obtained by either method is then transferred to the smelting circuit to produce gold bullion.
Gold extraction
Carbon in pulp
Gold extraction
2) Merrill-Crowe process Merrill Crowe
Gold recovery:
Traditional method for Au recovery from pregnant cyanide solutions. Once dissolution of Au is complete, the remaining rock pulp if filtered off through various filters & diatomaceous earth to produce a sparkling clear solution. O2 is removed from the clarified solution by passing the solution through a vacuum deaeration column.
Gold extraction
2) Merrill-Crowe process Merrill Crowe
Gold recovery:
Zinc dust is then added to the cyanide solution to chemically reduce the gold to the metal. The metallic gold is then filtered out & refined.

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Extraction Metallurgy

Part 2: Case studies

Dr. C.B. Perry ( y (C306) )

Hydrophilic attracted H d hili tt t d to sulphide minerals

Potassium amyl xanthate

Typical Air Emissions

Typical Liquid Effluents T i l Li id Effl t

C i normally l Cu is ll leached b one of th h d by f three methods: th d

(2) dissolution of alkaline materials by acid:

R = alkyl ,phenyl, or H phenyl R1 = alkyl

An electrochemical process for precipitating metals from solution. f l ti

a) SEM of SiO2 powder b) reduced Si powder.

Red mud formation consumes dissolved Al and represents a Al loss.

Step 2: find the number of moles of electrons:

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