CHEMISTRYย OFย ALUMINIUMย PRODUCTION
THEย ORE
Aluminiumย isย extractedย fromย bauxiteย whichย containsย Al2O3.xH2Oย 
whereย xย =ย 1ย orย 3ย soย thatย theย formulaย isย sometimesย givenย asย 
Al2O3.2H2O.

PRIMARYย ORย SECONDARYย PRODUCTION
Aluminiumย productionย isย eitherย primaryย orย throughย 
recyclingย (secondary).ย Primaryย productionย isย energyย 
intensiveย andย recyclingย isย preferred,ย sinceย itย isย 
intensive and recycling is preferred since it is
cheaper.

Impuritiesย inย bauxiteย includeย oxidesย ofย Ti,ย Siย andย Feย whichย mustย beย 
removedย beforeย extractionย ofย aluminium.ย Varyingย amountsย ofย ironย 
oxideย giveย bauxiteย itsย coloursย whichย rangeย fromย whiteย (noย ironย oxide)ย  Primaryย aluminumย productionย involvesย obtainingย 
aluminaย (Al2O3)ย fromย bauxiteย forย electrolysisย whichย 
toย redย (upย toย 27%ย Fe2O3).
yieldsย theย metal.

SEPARATINGย ALUMINIUMย FROMย IMPURITIES
Aluminiumย separationย startsย withย digestionย ofย bauxiteย byย concentratedย NaOH.ย Thisย takesย advantageย ofย theย factย thatย Fe2O3 isย 
notย amphoteric asย isย Al2O3.ย Al2O3 isย thereforeย dissolvedย andย Fe2O3 isย removedย asย aย solidย byย filtration.ย Theย filtrateย containsย 
twoย mainย species:ย [Al(OH)4]โ€(aq) andย SiO32โ€(aq) whichย areย formedย asย follows:
Al2O3 +ย 2OHโ€ +ย 3H2Oย โ†’ 2[Al(OH)4]โ€ and SiO2(s) +ย 2OHโ€(aq) โ†’ SiO32โ€ +ย H2O
Theย mixtureย isย dilutedย withย waterย orย treatedย withย CO2 toย precipitateย aluminiumย hydroxide:
2[Al(OH)4]โ€ + CO2 โ†’ 2Al(OH)3 + CO32โ€ + H2O โ€ Al(OH)3 is a white gelatinous solid
+ย CO
+ย CO 2 +ย H
isย aย whiteย gelatinousย solid.
Carbonย dioxideย formsย aย weakย acidย solutionย ofย carbonicย acidย thatย neutralizesย theย NaOH.ย Thisย neutralizationย selectivelyย 
precipitatesย Al(OH)3 butย leavesย theย remainingย tracesย ofย silicaย inย solution.
Anย alternativeย routeย ofย aluminiumย separation,ย notย involvingย useย ofย CO2 orย precipitationย ofย hydroxideย involvesย twoย stepsย 
whereย conditionsย areย adjustedย toย promoteย theย sameย reactionย inย differentย directionsย asย required.
1. Dissolvingย toย allowย separationย ofย aluminumย fromย impurities:ย ย Al2O3.xH2Oย +ย 2NaOHย โ†’ 2NaAlO2 +ย (x+1)H2O
2. Afterย filtrationย theย reactionย isย reversed:ย 2NaAlO2 +ย 2H2Oย โ†’ 2NaOHย +ย Al2O3.3H2O (reversalย isย achievedย byย coolingย andย 
seedingย withย crystalsย ofย Al2O3.3H2O).ย Thisย methodย producesย fineย particlesย ratherย thanย aย gelatinousย mass.

CALCINATIONย 
Thisย isย aย termย whichย meansย heatingย toย aย highย temperatureย withoutย 
meltingย soย thatย hydrates,ย carbonatesย orย otherย compoundsย areย 
decomposedย andย theย volatileย materialย isย expelled.ย Whetherย aluminaย orย 
aluminiumย hydroxideย haveย beenย obtainedย inย theย separation,ย theย nextย 
stepย isย calcinationย atย 400ย toย 1200ย  Cย (averageย 1000ย  C)ย toย giveย Al
step is calcination at 400 to 1200 ยฐC (average 1000 ยฐC) to give Al2O3:
2Al(OH)3 โ†’ Al2O3 +ย 3H2O or Al2O3.3H2Oย โ†’ Al2O3 +ย 3H2O.

ELECTROLYSIS

CRYOLITE
Cryoliteย (Na3AlF6)ย isย aย solventย forย alumina.ย Itย alsoย 
servesย toย lowerย theย meltingย pointย ofย theย mixtureย toย 
1000ย fromย 2000ย ยฐC forย pureย aluminaย soย thatย 
electrolysisย isย lessย costlyย (consumesย lessย electricalย 
electrolysis is less costly (consumes less electrical
energy).

Cathodeย reaction:ย ย Al3+ +3eโ€ โ†’ Al
Primaryย anodeย reaction:ย ย 2O2โ€ โ€ 4eโ€ โ†’ O2
Secondaryย (nonย electrolytic)ย anodeย reaction:ย Cย +ย O2 โ†’ CO2
Overallย cellย reactionย isย 2Al2O3 +ย 3Cย โ†’ 4Alย +ย 3CO2
Fromย theย overallย reactionย itย canย beย seenย thatย carbonย playsย 
p y
aย veryย indirectย roleย asย aย reducingย agent.
Duringย electrolysisย energyย isย requiredย toย bothย dischargeย 
ionsย andย maintainย theย electrolyteย inย aย moltenย state.
Smelting isย aย processย ofย metalย extractionย atย highย 
temperatureย (pyrometallurgy).ย Itย involvesย meltingย theย 
concentratesย fromย metalย oresย toย removeย impuritiesย andย 
toย reduceย metalย compoundsย toย metals.ย Examplesย ofย 
to red ce metal compo nds to metals E amples of
smeltingย includeย theย extractionย ofย ironย inย aย blastย furnaceย 
andย aluminiumย extractionย byย electrolysisย ofย aย melt.

Putย Togetherย Byย Denisonย Atย Globalย Inย Cunupia.ย 739โ€2656.

Cape Unit 2 Module 3 Aluminium Extraction Cram Sheet

  • 1.
    CHEMISTRYย OFย ALUMINIUMย PRODUCTION THEย ORE Aluminiumย isย extractedย fromย bauxiteย whichย containsย Al2O3.xH2Oย  whereย xย =ย 1ย orย 3ย soย thatย theย formulaย isย sometimesย givenย asย  Al2O3.2H2O. PRIMARYย ORย SECONDARYย PRODUCTION Aluminiumย productionย isย eitherย primaryย orย throughย  recyclingย (secondary).ย Primaryย productionย isย energyย  intensiveย andย recyclingย isย preferred,ย sinceย itย isย  intensive and recyclingis preferred since it is cheaper. Impuritiesย inย bauxiteย includeย oxidesย ofย Ti,ย Siย andย Feย whichย mustย beย  removedย beforeย extractionย ofย aluminium.ย Varyingย amountsย ofย ironย  oxideย giveย bauxiteย itsย coloursย whichย rangeย fromย whiteย (noย ironย oxide)ย  Primaryย aluminumย productionย involvesย obtainingย  aluminaย (Al2O3)ย fromย bauxiteย forย electrolysisย whichย  toย redย (upย toย 27%ย Fe2O3). yieldsย theย metal. SEPARATINGย ALUMINIUMย FROMย IMPURITIES Aluminiumย separationย startsย withย digestionย ofย bauxiteย byย concentratedย NaOH.ย Thisย takesย advantageย ofย theย factย thatย Fe2O3 isย  notย amphoteric asย isย Al2O3.ย Al2O3 isย thereforeย dissolvedย andย Fe2O3 isย removedย asย aย solidย byย filtration.ย Theย filtrateย containsย  twoย mainย species:ย [Al(OH)4]โ€(aq) andย SiO32โ€(aq) whichย areย formedย asย follows: Al2O3 +ย 2OHโ€ +ย 3H2Oย โ†’ 2[Al(OH)4]โ€ and SiO2(s) +ย 2OHโ€(aq) โ†’ SiO32โ€ +ย H2O Theย mixtureย isย dilutedย withย waterย orย treatedย withย CO2 toย precipitateย aluminiumย hydroxide: 2[Al(OH)4]โ€ + CO2 โ†’ 2Al(OH)3 + CO32โ€ + H2O โ€ Al(OH)3 is a white gelatinous solid +ย CO +ย CO 2 +ย H isย aย whiteย gelatinousย solid. Carbonย dioxideย formsย aย weakย acidย solutionย ofย carbonicย acidย thatย neutralizesย theย NaOH.ย Thisย neutralizationย selectivelyย  precipitatesย Al(OH)3 butย leavesย theย remainingย tracesย ofย silicaย inย solution. Anย alternativeย routeย ofย aluminiumย separation,ย notย involvingย useย ofย CO2 orย precipitationย ofย hydroxideย involvesย twoย stepsย  whereย conditionsย areย adjustedย toย promoteย theย sameย reactionย inย differentย directionsย asย required. 1. Dissolvingย toย allowย separationย ofย aluminumย fromย impurities:ย ย Al2O3.xH2Oย +ย 2NaOHย โ†’ 2NaAlO2 +ย (x+1)H2O 2. Afterย filtrationย theย reactionย isย reversed:ย 2NaAlO2 +ย 2H2Oย โ†’ 2NaOHย +ย Al2O3.3H2O (reversalย isย achievedย byย coolingย andย  seedingย withย crystalsย ofย Al2O3.3H2O).ย Thisย methodย producesย fineย particlesย ratherย thanย aย gelatinousย mass. CALCINATIONย  Thisย isย aย termย whichย meansย heatingย toย aย highย temperatureย withoutย  meltingย soย thatย hydrates,ย carbonatesย orย otherย compoundsย areย  decomposedย andย theย volatileย materialย isย expelled.ย Whetherย aluminaย orย  aluminiumย hydroxideย haveย beenย obtainedย inย theย separation,ย theย nextย  stepย isย calcinationย atย 400ย toย 1200ย  Cย (averageย 1000ย  C)ย toย giveย Al step is calcination at 400 to 1200 ยฐC (average 1000 ยฐC) to give Al2O3: 2Al(OH)3 โ†’ Al2O3 +ย 3H2O or Al2O3.3H2Oย โ†’ Al2O3 +ย 3H2O. ELECTROLYSIS CRYOLITE Cryoliteย (Na3AlF6)ย isย aย solventย forย alumina.ย Itย alsoย  servesย toย lowerย theย meltingย pointย ofย theย mixtureย toย  1000ย fromย 2000ย ยฐC forย pureย aluminaย soย thatย  electrolysisย isย lessย costlyย (consumesย lessย electricalย  electrolysis is less costly (consumes less electrical energy). Cathodeย reaction:ย ย Al3+ +3eโ€ โ†’ Al Primaryย anodeย reaction:ย ย 2O2โ€ โ€ 4eโ€ โ†’ O2 Secondaryย (nonย electrolytic)ย anodeย reaction:ย Cย +ย O2 โ†’ CO2 Overallย cellย reactionย isย 2Al2O3 +ย 3Cย โ†’ 4Alย +ย 3CO2 Fromย theย overallย reactionย itย canย beย seenย thatย carbonย playsย  p y aย veryย indirectย roleย asย aย reducingย agent. Duringย electrolysisย energyย isย requiredย toย bothย dischargeย  ionsย andย maintainย theย electrolyteย inย aย moltenย state. Smelting isย aย processย ofย metalย extractionย atย highย  temperatureย (pyrometallurgy).ย Itย involvesย meltingย theย  concentratesย fromย metalย oresย toย removeย impuritiesย andย  toย reduceย metalย compoundsย toย metals.ย Examplesย ofย  to red ce metal compo nds to metals E amples of smeltingย includeย theย extractionย ofย ironย inย aย blastย furnaceย  andย aluminiumย extractionย byย electrolysisย ofย aย melt. Putย Togetherย Byย Denisonย Atย Globalย Inย Cunupia.ย 739โ€2656.