Mn Ore Reduction Technologies

Mrs.MadeleinTodd MarketAnalyst&MetallurgicalEngineer ConsultingtoManganeseMetalCompany

7th IMnIEPDChinaConference 23March2010 Nanning,Guangxi

Content
Introductiontoreduction WheredoesreductionfitintotheEMMorEMDprocessflow? Mainreductionreactions Overviewofavailabletechnologiesandequipment Reductiveleaching Summary

EMM and EMD production requires soluble manganese ore

Hydrometallurgicalprocessroutetoobtain highpurityendproduct needsorethatis solubleinsulphuricacid. Themoststableoxidationstatefor manganeseis+2,whichhasapinktored colour.Thisisalsothemostsolublestate. Thisoxidationstateisseeninthemineral rhodochrosite,MnCO3,ormanganese(II) carbonate.Orecontainingthismineralcan beleachedasis. However,mostoresofmanganesedont containmanganese(II)buthigheroxides, whicharenot soluble: MnO2 pyrolusite manganese(IV) Mn2O3 bixbyite manganese(III) Mn3O4 hausmannite manganese(II,III) Mn7SiO12 braunite manganese(II,III)
[BraunitealsocontainsCainsomedeposits]

Pourbaix diagram for Manganese: c(Mn) = 1 mol/l, T = 25 C

Oxide ore must be reduced before leaching: add heat and a reductant
Thehigheroxidationstates(IV)and(III)mustbereducedto(II)byusingasuitablereducing agent,beinghydrogenorcarbonortheircompounds. Thetemperaturemustbeincreasedtoover~850Cbeforethereactionswilltakeplace. Typicalreductantsarebituminouscoal,heavyfurnaceoil,naturalgasorliquefiedpetroleum gas.Thereductantmustbegaseousatthetemperatureofthereductionprocess.Higher hydrocarbons,e.g.kerosene,mustfirstbecrackedintolowerchainmolecules. Theamountofreductantusedmayvarywidely,butmustbeabovethestoichiometricamount necessarytoreducethemanganeseoxidestoMnO.Thereductantconcentrationmaybe controlledviavariousmeans,e.g.bymonitoringtheexitgascompositionorthemanganous contentofthedischargesolids. ThesequenceofreductionisMnO2 Mn2O3 Mn3O4 MnO.Ineachstepanothermole ofoxygenisremoved. Afterthereduction,theoremustbecooledinanonoxidizingatmosphere(inertorreducing), topreventspontaneousreoxidationoftheMnO.Thefinaldischargetemperaturemustbe 100Corless. Anothertermforreductionisroasting.

Typical reduction reactions

Mostofthereductionreactionsareexothermic,buttheyhavefairlyhighactivationenergythatmust beovercomefirst.Reactionstypicallystartabove800Conly. Othertypicalreactionsduringorereduction:

TheBoudouard reaction:CO2(g) +C(s) 2CO(g) ThewatergasformationreactionH2O(g) +C(s) CO(g) +H2(g) Thesewillconvertsolidreductantintogaseousreductantorviceversa. Also,decompositionofMnOOHtoMn2O3 willtakeplacewithoutconsuminganyreductant. Crackingofhigherhydrocarbonsdontconsumereductantoroxygen.

Theefficiency ofthereductionreactionsareimprovedifthereductantisagas,theore particlesizeisverysmallandgoodsurfacecontactisensuredbetweenoreandgas.All reagentsmustbeatthetemperaturerequiredforthereactionstostart.Atlower temperaturesalongretentiontimeisneeded.

Thermodynamics of Mn ore reduction

Change in free energy (G kcal/mole)
Mn2O3plusH Mn2O3plusCO Mn3O4plusCO Mn3O4decomposition Boudouard

100 80 60 40 20 0
0
Temperature inCelsius

100

200

300

400

500

600

700

800

900

1000

1100

1200

20 40 60

Reactionswillonlytakeplaceiftheyresultinaloweringofthetotalfreeenergy(G) ofthereagents andproducts.Freeenergyisafunctionoftemperatureandisuniqueforeveryreaction. Theactivationenergyforeachreactionmustalsobeovercomebeforethereactionstartstotakeplace, evenifitisanexothermicreaction.

Additional step in process flow

Differenttechnologiescanbeusedto achievetheorereductionstep:
Reverberatoryfurnace Calcining Microwavefurnace Heapreduction Shaftfurnace Singleormultiplehearthfurnace Fluidizedbedreactor Customdesigns/combinationsofabove
TypicalprocessflowforElMnorEMDproduction

Anotherpossibilityforusingoxideoreisto performreductiveleaching(i.e.leach directlyfromhigheroxidationstateto2+). Inthiscasenoadditionalprocessstepis required,i.e.nofurnaceneeded. Thebalanceofthispresentationwillbriefly touchonsomeofthesetechnologies.

Reverberatory furnace
Theoreisseparatedfromthefuelbut isincontactwiththecombustion gases.Bituminouscoalisatypicalfuel. Oldtechnology.Usedforcopperor leadinmiddleages.UsedinJapanfor ironmakingin18th century,was replacedbytheblastfurnace. Currentlyusedmostlyinsecondary aluminium(scrap)industry,for smeltingbeforediecasting. UsedinChinaatanumberofElMn factoriestoreduceMnoxideore. Iftheexhaustgasisnotcollectedand combustedfully,thisprocessis potentiallyhighlypolluting. Disadvantages: Difficulttomaximiseheattransferduetothe spatialseparationoftheburningfuelandtheore. Exhaustgaschemistrymustbecontrolledto maintainareducingmixtureinthechamber. Poorcontactbetweenoreandreductantsdueto orebeingastationarybed.

Calcining

Microwave furnace
Sameprincipalandlayoutascalcining, butthesourceofheatismicrowaves. Thereductant(coaloroil)isstilladded withtheoreintotherotatingtube. Efficiencyoftheprocessdependsonthe designofthemagnetronandthe presenceofagoodsusceptor amaterial whichheatsupwhenexposedto microwaves.Graphiteisagood susceptor.Atmospheremustbe controlledsimilartocalcining. Microwavesheatonlythesubstance beingreducedandnottheatmosphere arounditorthefurnacewalls.This makesishighlyenergyefficient. Withasmallerphysicalfootprintanda substantiallysmallercarbonfootprint, microwavefurnacesofferfarlower operatingcoststhancalcinersor reverberatoryfurnaces.

Internal parts of a magnetron same design for domestic or industrial equipment

Disadvantages: Thisisfairlynewtechnologythathasnotyet beenprovedonindustrialscaleforthe manganeseindustry. Choiceofreductantislimitedduetoneedfor asusceptorandabsenceofhotgasstream.

Heap reduction (also called pile roasting)

Simplestmethodofreductionavailable nosignificantequipmentinstallation required,onlygaspipingsystem. ThismethodwasusedatKerrMcGees EMMfactoryinUSA(closedin2001). Naturalgasisthesourceofheatand thereductant.Substoichiometric combustionofthegasprovidesheat andleaveshydrocarbonsavailablefor reduction. Temperatureinsidepilemustbeinthe 700 to900Crange.Mostsuitablefor highgradeore exothermicreactions. Batchprocess,usuallyfollowedby polishingstepinverticalbins.
Ore heap 8ft high, 16ft wide

Ground level Gas supply

Trench with piping system above ground, burner nozzles at intervals

Disadvantages: Pollutioncontrolisalmostimpossible Affectedbyinclementweather Longretentiontimeof1to2days Cannotusefines Clinkerformationathotspots

Fluidized bed reactor

Airstreamispassedthroughaperforated plateatthebottomofaverticalreaction chamber,intowhichoreisfedon continuousbasis. Fineparticlessuspendedinhotgasstream allowscompletereduction. Quenchedslurrycanbepumpeddirectlyto leachtanks. Reductantcanbegasorcoalpartially combustedinseparatechamber. Efficientuseofreductant,recirculation.

Disadvantages: Expensivetoinstall.Needstandby blower. Longdelaybetweenstartupandstable stateoperation. Controlofparticlesizeiscritical.

Reductive leaching
Alternativetohightemperaturereductive roasting. MnO2 oreisdissolveddirectlyindilute sulphuricorhydrochloricacidinthepresence ofasuitablereducingagent,e.g.:sulphur dioxide,ferroussulphateorferrouschloride, hydrogenperoxide,elementaliron,cane molasses,etc. Standardleachtankdesignwithprewetter, agitatorandventilation. Processefficiencyisaffectedbytemperature, particlesizeofore,concentrationofreducing agent,andconcentrationofacid.

Reductive leaching test results example

ExperimentalCondition Reductantused Temperature Particlesizeofsolids
Effectofacidtoore(A/O)molarratioondissolution efficiencyofmanganesedioxide.20C,particlesize 250+150m,irontoore(I/O)molarratio0.8.

Testsby Bafghietal

Testsby Zakerietal

Spongeiron Ferrousion powder 20C 250+150 m 3.0 0.8 20C 250+150 m 3.0 2.4 80% 92% (30mins)

H2SO4/MnO2molar ratio Fe/MnO2molarratio

Mndissolutionefficiency 98% after10mins Maximumdissolution efficiency 100% (15mins)

Effectoforeparticlesizeondissolutionefficiencyof manganesedioxide.20C,A/O=4.0,I/O=2.0.

Source:Bafghi,M.S.,Zakeri,A.,Ghasemi,Z.,Adeli,M.,2007. Reductivedissolutionofmanganeseoreinsulphuricacidinthe presenceofironmetal.Hydrometallurgy90(2008),207212.

Reductive leaching
Disadvantages: TherelativelowpHthatisnecessarytoobtain dissolutionoftheMnwillleachoutmore impuritiescomparedtoconventionaloxidative leaching. Theaccesstoandcostofsuitablereductants arekeylimitationstothisprocess: SO2 resultsinneedforamanganese sulphatebleedstreamtomanagethe sulphatemassbalance Fe2+willprecipitatewhenpHisliftedafter leach,torecovertheFe2+willrequire roastingofthehydroxideprecipitate Scrapirondoesnothavesufficientsurface areaandatomisedorspongeironis expensive.

Summary
Mostofthemanganeseoresoftheworldareoxidemineralsthatarenot solubleduetothehigheroxidationstate.Thisincludesthehighgrade (>40%Mn)oreproducedinAustraliaandSouthAfrica. OrechoicesforaproducerofEMMorEMD:
Uselowgradecarbonateorewithoutanyneedforreduction. Usehighgradeoxideorebutaddareductionstepbeforeleaching.

Variousdifferenttechnologiescanbeemployedtoachievereductionof oxideore,eachhasbenefitsanddisadvantages. Laboratoryorpilotscaletestingofanoretypeisneededbeforethe optimaltechnologychoicecanbemade. Availabilityofaccurateoremineralogydataissometimeslimited.

Contact details
Formoreinformationorgeneraldiscussion,youcancontactmeat: Mrs.MadeleinTodd mtodd@telkomsa.net Phone+27137458367or+27828838180 ForcontactingmeinChinese,pleasedoitviaMr.HuBo,whowillbeable totranslateandforwardyourmessage: Mr.HuBo mmchubo@hotmail.com Phone+8613541046757