Extraction Metallurgy完整版.ppt

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1、Extraction MetallurgyPart 2:Case studiesDr.C.B.Perry(C306)Extraction MetallurgyPart 2:Case studiesCopper Pyrometallurgy route and environmental concerns.The hydrometallurgical alternative.Hydrometallurgicalprocesses ion exchange processes,solvent extraction,and bacterial leaching.Iron Pyrometallurgy

2、 and the blast furnace.Silicon The electric arc furnace.Purification by the Czochralski process.Aluminium Electrolytic reduction.Thesiderophiles The extraction of Au and the Pt group metals and their purification.Pyrometallurgy of copperReminder:Pyrometallurgy is the use of heat to reduce the minera

3、l to the free metal,and usually involves 4 main steps:1.Calcination:thermal decomposition of the ore with associated elimination of a volatile product.2.Roasting:a metallurgical treatment involving gas-solids reactions at elevated temperatures.3.Smelting:a melting process which separates the chemica

4、l reaction products into 2 or more layers.4.Refining:treatment of a crude metal product to improve its purity.Pyrometallurgy of copperCu 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 importa

5、nt ores include:chalcocite Cu2S,malachite CuCO3 Cu(OH)2,azurite 2CuCO3 Cu(OH)2,bornite(3Cu2S Fe2S3),covellite(CuS).Pyrometallurgy of copperThe following steps are involved in Cu extraction:1.Concentration2.Roasting3.Smelting4.Conversion5.RefiningPyrometallurgy of copper1.ConcentrationFinely crushed

6、ore concentrated by the froth-flotation process:Ground ore mixed with xanthates(salts&esters of xanthic acid),dithiophosphates,or thionocarbamates.These make the ore surface hydrophobic.Ore then introduced into a water bath where air is bubbled through the suspension.Finely divided hydrophobic ore p

7、articles latch on to the air bubbles and travel to the surface where a froth is formed.Pyrometallurgy of copper1.Concentration(cont.)The froth containing the Cu ore is skimmed off and reprocessed.The remaining material(sand particles&other impurities)sink to the bottom&is discarded or reprocessed to

8、 extract other elements.Pyrometallurgy of copper1.Concentration(cont.)Froth-flotationPyrometallurgy of copper2.RoastingInvolves 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(

9、s)+2Fe2O3(s)+8SO2(g)Reactions are exothermic,roasting is an autogenous process requiring little or no additional fuel.NB,not all the sulphides are oxidised,only around 1/3.Rest remain as sulphide minerals.The gases produced contain around 5 15%SO2,which is used for sulphuric acid production.Pyrometa

10、llurgy of copper2.Roasting(cont.)Objectives of roasting:1)Remove part of the sulphur.2)Convert iron sulphides into iron oxide and iron sulphate to facilitate removal during smelting.3)To pre-heat the concentrate to reduce amount of energy needed by the smelter.Pyrometallurgy of copper3.SmeltingSmelt

11、ing consists of melting the roasted concentrate to form 2 molten phases:1)a sulphide“matte”,which contains the iron-copper sulphide mixture.2)an oxide slag,which is insoluble in the matte,and contains iron oxides,silicates,and other impurities.Smelting is carried out at around 1200C,usually with a s

12、ilica 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.Pyrometallurgy of copper3.Smelting(cont.)The main reaction is the reduction of copper oxides(formed during roasting)back into copper sulphide to ensure t

13、hat 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)Pyrometallurgy of copper4.ConversionAfter smelting,matte contains from between 30 to 80%Cu in the form of copper sulphide.The sulphur is removed by selective oxidation

14、 of the matte with O2 to produce SO2 from S,but leave Cu metal.Converting is carried out in two stages:1)an iron removal stage,and 2)a copper-making stage.Pyrometallurgy of copper4.Conversion(cont.)IronremovalA silica flux is added to keep the slag(see below)molten.Air is blown into the converter to

15、 oxidize the iron sulphide according to the following reaction:2Cu2SFeS(l)+3O2(g)+SiO2(l)2FeOSiO2(l)+2SO2(g)+Cu2S(l)The oxidized Fe and Si form a slag(insoluble in matte)that is skimmed off&disposed off.CoppermakingThe sulphur in the Cu2S can now be oxidized to leave behind metallic copper according

16、 to the following reaction:Cu2S(l)+O2(g)2Cu(l)+SO2(g)The end product is around 98.5%pure&is known as blister copper because of the broken surface created by the escape of SO2 gas.Pyrometallurgy of copper4.Conversion(cont.)Pyrometallurgy of copper5.RefiningThe copper is refined by electrolysis.The an

17、odes(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.Cu2+ions migrate through the electrolyte to the cathode,where Cu metal plates out.Pyrometallur

18、gy of copper5.Refining(cont.)Metallic impurities more active then Cu are oxidized at the anode,but dont plate out at the cathode.Less active metals are not oxidized at the anode,but collect at the bottom of the cell as a sludge.The redox reactions are:Cu(s)Cu2+(aq)2e-Cu2+(aq)+2e-Cu(s)Ered=-0.83VPyro

19、metallurgy of copper5.Refining(cont.)Pyrometallurgy of copperEnvironmental impactLarge amount of gases produced present air pollution problems,in particular SO2 gas acid rain.Dust produced contains heavy metals such as mercury,lead,cadmium,zinc health problems.Waste water contaminated with:Insoluble

20、 substances,mostly waste sludge(finely ground rock).Soluble substances(heavy metals,sulphates).Chemicals from flotation process.Hydrometallurgy of copperAdvantagesMuch more environmentally friendly than pyrometallurgy.Compared to pyrometallurgy,only a fraction of the gases liberated into the atmosph

21、ere.Emissions of solid particles comparatively non-existent.DisadvantagesLarge amount of water used,greater potential for contamination.Waste waters contain soluble metal compounds,chelating compounds&organic solvents.Hydrometallurgy of copperThe following steps are involved:1.Ore preparation2.Leach

22、ing3.Solution purification4.Metal recoveryHydrometallurgy of copper1.Ore preparationOre undergoes some degree of comminution(crushing&pulverisation)to expose the Cu oxides&sulphides to leaching solution.Hydrometallurgy of copper1.Ore preparation(cont.)Amount of comminution depends on quality of ore:

23、Higher grade ore more comminution.Lower grade ore less comminution.(Why?)If possible,ore is pre-concentrated;reject ore that contains very little Cu.Hydrometallurgy of copper2.LeachingDefinition:The dissolution of a mineral in a solvent,while leaving the gangue(rock or mineral matter of no value)beh

24、ind as undissolved solids.Cu is normally leached by one of three methods:(a)Dump leaching(b)Heap leaching(c)Bacterial leachingHydrometallurgy of copper2.Leaching(cont.)(a)Dump leachingLeaching solution trickled over a dump.Runoff solution collected&the Cu recovered from it.A slow process that takes

25、months or years to complete.Typically only around 60%of the Cu in the dump is recovered.Hydrometallurgy of copper2.Leaching(cont.)(b)Heap leachingSimilar to dump leaching except ore not simply dumped on a hillside,but is crushed to gravel size&piled onto an artificial pad.After leaching(6 months to

26、1 year)gangue is removed from pad,disposed of&replaced with fresh ore.Hydrometallurgy of copper2.Leaching(cont.)LeachingreactionsNature of ore determines if leaching is non-oxidative or oxidative.Non-oxidativeleaching:No change in oxidation state.e.g.(1)dissolution of copper sulphate by water:CuSO4(

27、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)Hydrometallurgy of copper2.Leaching(cont.)Oxidativeleaching:Many ores only soluble once oxidised.e.g.covellite(CuS)much more soluble if oxidised to CuSO4CuS(s)+O2(g)CuSO4(aq)CLAS

28、S EXERCISE:work out which species is oxidised,and which is reduced,and write out the balanced half reactions for each.SOLUTION:CuS Cu=+2,S=-2O2 O=0CuSO4 Cu=+2,O4=-8,S=+6S-2 S+6+8e-(oxidation)2O2+8e-4O2-(reduction)Hydrometallurgy of copper2.Leaching(cont.)(c)Bacterial leachingSeveral bacteria,especia

29、lly Thiobacilli,are able to solubilise metal minerals by oxidising ferrous to ferric iron,as well as elemental sulphur,sulphide,and other 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.Very slow proc

30、ess;takes years for good recoveryBut low investment and operating costs.Hydrometallurgy of copper2.Leaching(cont.)(c)Bacterial leachingThiobacilliAre acidotolerant;some grow at pHs as low as 0.5Are tolerant against heavy metal toxicity.Are chemolithoautotrophs(C source is CO2&energy derived from che

31、mical transformation of inorganic matter).Hydrometallurgy of copper2.Leaching(cont.)MechanismsGeneralised reaction:M(II)S+2O2 M2+SO42-Two mechanisms:(a)indirect mechanism involving the ferric-ferrous cycle,and(b)direct mechanism involving physical contact of the organism with the sulphide mineral.(c

32、)Bacterial leachingHydrometallurgy of copper2.Leaching(cont.)Mechanisms:IndirectFirst step:ferrous sulphate is converted into ferric sulphate by the action of Acidithiobacillus ferrooxidans:(c)Bacterial leaching4FeSO4+O2+2H2SO4 2Fe2(SO4)3+2H2OCLASS EXERCISE:work out which is ferric-and which is ferr

33、ous sulphate,and write out the balanced half reactions for each.FeSO4 SO42-Fe2+(ferrous)2Fe2(SO4)3 3 SO42-=-6,but 2 Fe Fe3+(ferric)Hydrometallurgy of copper2.Leaching(cont.)Mechanisms:Indirect(c)Bacterial leaching2Fe2+2Fe3+2e-(oxidation)O2+2e-2O2-(reduction)Ferric sulphate is a strong oxidising agen

34、t capable of dissolving a range of sulphide minerals.In the case of chalcopyrite:CuFeS2+2Fe2(SO4)3 CuSO4+5FeSO4+2SHydrometallurgy of copper2.Leaching(cont.)Mechanisms:Indirect(c)Bacterial leachingThe elemental S produced by the indirect method can be converted to H2SO4 by Acidithiobacillus ferrooxid

35、ans:The H2SO4 helps maintain the pH at levels favourable for bacterial growth.Hydrometallurgy of copper2.Leaching(cont.)Mechanisms:Direct(c)Bacterial leachingBacteria actually adheres to the mineral surface prior to enzymatic attack.The mineral is oxidised with oxygen to sulphate and metal cations w

36、ithout any detectable intermediate occurring.In the case of covellite:CuS+2O2 CuSO4Hydrometallurgy of copper3.Solution PurificationLeaching reactions not perfectly selective other elements in solution as well,not just Cu.These need to be removed.After leaching,Cu in solution can be very dilute.need

37、a way to concentrate it.Both of these are generally done using ion exchange processes,the two most common being ion exchange chromatography,and solvent extraction.Hydrometallurgy of copper3.Solution PurificationIonexchangechromatographyDEFINITION:a solution containing a mixture of metal ions is cont

38、acted with a resin that is insoluble 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 that exchange with cations(M+)or anions(M),respectively.The ion-exch

39、ange process is reversible.Hydrometallurgy of copper3.Solution PurificationIonexchangechromatographyCarboxyl groups exchanges the ion it currently holds(H+)for a Cu2+ion.The Cu2+is later released by contacting it with a stripping solution(very high H+conc.).Hydrometallurgy of copper3.Solution Purifi

40、cation:SolventextractionDEFINITION:a method to separate compounds based on their relative solubilities in 2 different immiscible liquids.In industry,this is usually set up as a continuous processHydrometallurgy of copper3.Solution Purification:SolventextractionHydrometallurgy of copperOrganic+aqueou

41、s stream pumped into a mixer.Organic(containing an extractant)and aqueous components mix,and ion transfer occurs between them.Once ion transfer is complete(equilibrium),mixture is allowed to separate.Aqueous solution is removed&the organic phase(containing the Cu2+)is mixed with an aqueous stripping

42、 solution.Cu2+moves back into the aqueous 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.3.Solution Purification:SolventextractionHydrometallurgy of copperThe most successful extractants

43、for copper are of the ortho-hydroxyoxime type:R=alkyl,phenyl,or HR1=alkylFunction by means of a pH-dependent cation-exchange mechanism:Cu2+2HA CuA2+2H+3.Solution Purification:Solventextraction(where H in HA denotes the replaceable,phenolic proton)ExtractantsHydrometallurgy of copper3.Solution Purifi

44、cation:SolventextractionAt low pH(1.5 2.0)the ortho-hydroxyoxime extractant complexes the Cu.During back-extraction(stripping stage)the pH is lowered further,releasing the Cu,and regenerating the hydroxyoxime for recycle to the extraction stage.Aqueous feeds(leach solution)typically contain more iro

45、n per litre than copper.For commercial success,the extractant must have a greater selectivity for Cu than Fe.ExtractantsHydrometallurgy of copper3.Solution Purification:SolventextractionExtractantsCu2+forms square-planar complexes with hydroxyoxime:H-bonding between the oximic H and the phenolic O a

46、ffords this 2:1 complex unusual stability.The formation constant(K2)for the 2:1 complex is much greater than for the 1:1 complex.Hydrometallurgy of copper3.Solution Purification:SolventextractionExtractantsThe tris(salicylaldoximato)iron(III)complex is octahedral,and no extended planar ring structur

47、e 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.Hydrometallurgy of copper4.Metal Recovery:At this point,the metal needs to be recovered f

48、rom solution in the solid form.This is either achieved chemically,or electrochemically.Hydrometallurgy of copper4.Metal Recovery:Dissolved copper will plate out on an iron surface according to the following reaction:ChemicalrecoveryCu2+(aq)+Fe(s)Fe2+(aq)+Cu(s)Why?Reduction half-reactions:Cu2+(aq)+2e

49、 Cu(s)Ered=+0.34 VFe2+(aq)+2e Fe(s)Ered=-0.44 VEred for the Cu2+half-reaction is more positive than for the Fe2+half reaction which leads to Cu being reduced and Fe oxidised.Hydrometallurgy of copper4.Metal Recovery:Solutions containing dissolved copper are thus run through a bed of shredded scrap i

50、ron,resulting in the copper ions being plated out as solid Cu on the iron surface.For the process to be efficient,the surface of the scrap iron must be large.ChemicalrecoveryHydrometallurgy of copper4.Metal Recovery:An electrochemical process for precipitating metals from solution.Electrochemicalrec