The Chemistry and Processing of Jamaican Bauxite

The first commercial extraction of alumina (Al2O3) from bauxite has been attributed to Henri Sainte-Claire Deville in about !"#$ Soon after this% in !!!% &arl 'ose(h )a*er described +hat is no+ ,no+n as the )a*er -rocess% +hich led to a dramatic reduction in the cost of aluminum metal$ Toda*% it is an ever*da* commodit*% rather than a (recious metal$ Althou.h de(osits of aluminous red earth have been ,no+n to occur in the Tertiar* /imestone areas (+hich covers t+o thirds of the land surface of 'amaica) since the !201s% it +as not until the 2#01s that their economic si.nificance as an ore of aluminum +as reco.nised$ 3n October% 2#3% Alcan +as incor(orated under the name 'amaica )auxites /imited as a 'amaican com(an* to investi.ate the commercial (otential of 'amaican bauxite$ 3n the same *ear% 2"00 tonnes of ore +as shi((ed to the 4SA for (rocess investi.ation and it +as realised that the bauxite +as suitable for (rocessin. usin. )a*er technolo.*$ The &ir,vine +or,s +ere com(leted around 2"2 and the first shi(ment of alumina +as consi.ned to a 5or+e.ian smelter in 'anuar* 2"3$

A )a*er (lant in 'amaica The )a*er -rocess% +hich continues to be the most economical method of manufacturin. alumina can be schematicall* summarised in a flo+ chart%

and involves the follo+in. o(erations6

-minin. -dissolution of the alumina at elevated tem(eratures -addition of flocculants -(reci(itation of (ure 7ibbsite -re.eneration of the solutions for rec*clin. -heatin. the 7ibbsite to 00C (calcination) to .ive alumina

Mining
3mmediatel* (rior to minin. an* de(osit% the land is cleared and the to( soil% to a minimum of 8 inches% removed and stoc,(iled for later re(lacement +hen minin. is com(leted$ The surface occurrence of the ore (usuall* less than 00 feet) ma,es the de(osits suitable for minin. b* sim(le o(encast methods$ Due to the soft% earth* nature of the ore% no drillin. or blastin. is .enerall* re9uired$ De(osits are located in areas var*in. from .entle undulatin. to ru..ed% hill* terrain involvin. ma:or ca(ital ex(enditures in establishin. a s*stem of ore trans(ortation$

;inin. areas in 'amaica

Dissolution of the alumina at elevated temperatures

The exact (rocedure re9uired for di.estion% de(ends on the nature of the ore de(osits$ The follo+in. Table outlines a number of minerals commonl* found in bauxites6 7ibbsite (h*drar.illite) )oehmite Dias(ore Hematite 7oethite ;a.netite Siderite 3lmenite Anatase =utile )roo,ite Hallo*site &aolinite >uart? -Al2O3$3H2O -Al2O3$H2O -Al2O3$H2O -<e2O3 -<eOOH <e3O# <eCO3 <eTiO3 TiO2 TiO2 TiO2 Al2O3$ 2SiO2$3H2O Al2O3$ 2SiO2$2H2O SiO2

'amaican bauxite is mainl* .ibbsitic but some amount of boehmite is also (resent$ The avera.e .rade of bauxite mined is of the order of #"@ available alumina and $"@ reactive silica$ 3n order to remove the iron oxides and most of the silicon oxides (resent% the ore is first treated +ith sodium h*droxide$ The di.estion (rocess ta,es advanta.e of the solubilit* of am(hoteric aluminum oxides to form a solution of aluminate ions% +hilst the basic iron oxides +hich form do not dissolve and are se(arated b* filtration$
Gibbsite Al2O3.3H2O Boehmiite Al2O3.H2O + 2NaOH ---> 2 NaAlO2 + 4 H2O (135-150 C) + 2NaOH ---> 2 NaAlO2 + 2 H2O (205-245 C)

Dias o!e Al2O3.H2O

+ 2NaOH ---> 2 NaAlO2 + 2 H2O (hi"h # a$% &)

Com(lete extraction from dias(oric bauxite re9uires stron.er caustic solutions% in addition to hi.her tem(eratures and (ressures$ 3n .eneral the reaction e9uilibria above move to the ri.ht +ith increases in caustic soda concentration and tem(erature$ 3n (ractice this means that for de(osits containin. the more easil* recovered 7ibbsite onl*% (roduction costs are much lo+er than +hen )oehmite or Dias(ore are (resent$ The control of silica in the conventional )a*er -rocess is most im(ortant and in fact ores havin. reactive silica .reater than A@ cannot be economicall* (rocessed$ 4nli,e 9uart?% +hich is considered virtuall* non-reactive at 7ibbsite extraction tem(eratures% some minerals% includin. ,aolins% dissolve ra(idl* and the reaction of the silica can .ive rise to a((reciable loss of caustic soda and aluminum$ The control of silica is .enerall* carried out durin.% or (rior to% the di.estion ste(% and .enerall* involves dissolution% e. for ,aolin
Al2O3.2'iO2 + NaOH ---> Na2'iO3

and desilication via (reci(itation$

Na2'iO3 + NaAlO2 ---> Na2O.Al2O3.2'iO2

Dissolution is necessar* to su(ersaturate the li9uid to a (oint +here the sodalite formed acts as a seed to (reci(itate more sodalite$ The rate of (reci(itation is found to increase +ith tem(erature% ho+ever at 3"- "0 C it is si.nificantl* slo+er than is re9uired for com(lete 7ibbsite extraction +hich occurs +ithin minutes$ The need for desilication therefore means that the material must be held at the di.estion tem(erature lon. enou.h to allo+ the silica to (reci(itate$ Still to come

Addition of Flocculants Precipitation of pure Gi !egeneration of solutions The !ed Mud Ponds site

and the latest ideas on dr* stac,in.

Calcination
=eferences$ see for exam(le% =$'$ /ancashire% B)auxite and aluminium (roductionB Cducation in Chemistr*% ;a* 2!2% ((s 82-8#$ -roduction fi.ures on )auxite from Dictoria in Australia are available at the 5ational =esources and Cnvironment +ebsite under 1;inerals and -etroleum1$ <or information on the )a*er -rocess see the ;ineral Council of Australia$ <urther information is available from 5abalco% =e*nolds or &aiser (bauxite and alumina minin. com(anies)$ <or the latest statistics on bauxiteEalumina (roduction chec, the 4S 7eolo.ical Surve*s site

Production Figures
Total bauxite (roduction fi.ures released b* the 'amaica )auxite 3nstitute are measured as crude bauxite (lus bauxite converted into alumina and in 22A reached 3 million tonnes for the first 9uarter$ This com(ared +ith a $A million for 228 and million tonnes in 22"$ The alumina (lants +ere said to be +or,in. at 28@ ca(acit* for the first time in man* *ears and for the first 9uarter ( 22A) (roduced ! 8%222 tonnes$ A descri(tion of the Hall (rocess for electrol*tic reduction of alumina to aluminum is a((ro(riatel* (rovided at Oberlin Colle.e% from +here Charles Hall had .raduated onl* ei.ht months (rior to his successful ex(eriment$
Home 'a themes /ab$ ;anuals /ectures Search Soft+are S(ectra Staff Tutorials 4F3-;ona Home Co(*ri.ht G 2003 b* =obert 'ohn /ancashire% all ri.hts reserved$ Created and maintained by Prof. Robert J. Lancashire, The Department of Chemistry, University of the West Indies, Mona Camp s, !in"ston #, Jamaica. Created <eb 22"$ /in,s chec,ed andEor last modified 28th 'anuar*% 2003$ "!# htt(6EE+++chem$u+imona$edu$:mElecturesEbauxite$html

A =e(lica of the Aluminum Ca( to the Fashin.ton ;onument /ocated in Fashin.ton DC$ On <ebruar* 23% !!8 in the +oodshed behind his famil*1s home at 8# Cast Colle.e Street in Oberlin% Charles ;artin Hall (roduced .lobules of aluminum metal b* the electrol*sis of aluminum oxide dissolved in a cr*olite-aluminum fluoride mixture$ This

achievement +as the culmination of several *ears of intensive +or, on this (roblem$ 3t +as a .oal that he had set as a hi.h school student and that had been encoura.ed +ith ideas and materials b* -rofessor <ran, <$ 'e+ett of Oberlin Colle.e$ Hall +as .raduated from Oberlin in 'une !!"% ei.ht months before the successful ex(eriment$ At the time of Hall1s discover* the onl* (ractical +a* to ma,e aluminum metal +as throu.h the chemical reduction of anh*drous aluminum chloride b* sodium metal at elevated tem(eratures$ The reaction is This (rocess +as a costl* one o+in. to the difficult* of (re(arin. +ater-free aluminum chloride from aluminum oxide% the natural source of aluminum% and to the necessit* of ma,in. sodium metal b* chemical means$( ) 3n the earl* !!01s aluminum +as a semi(recious metal% but 'e+ett had a sam(le of it to sho+ his students$ 5ot onl* did Hall have to devise a method for +innin. aluminum metal% but he also had to fabricate most of his a((aratus and (re(are his chemicals$ 3n his earl* ex(eriments he tried to ada(t the hi.h tem(erature carbon reduction methods that +ere used in the metallur.* of iron and other metals of intermediate chemical activit*$ He also tried to reduce the aluminum in cr*olite +ith sodium metal$ 3n subse9uent ex(eriments Hall% +or,in. in 'e+ett1s laborator* in Cabinet Hall% sho+ed that the electrol*sis of aluminum fluoride in +ater .ave onl* aluminum h*droxide$ The* understood that electrol*sis (rovided more (o+erful reduction conditions than did chemical methods$ Toda*% it is +ell ,no+n that h*dro.en in +ater is more easil* reduced than is aluminum ion$ The cathodic half reaction in the (resence of aluminum ion is The selection of aluminum fluoride for this ex(eriment +as (robabl* a turnin. (oint in Hall1s +or,$ 4sin. this substance +as certainl* not a matter of convenience because he had to (re(are it from ha?ardous h*dro.en fluoride in s(ecial lead vessels in 'e+ett1s laborator*$ ;ost li,el* Hall and 'e+ett chose to tr* the fluoride because it had not been tried before$ 5o doubt earlier ex(erimenters had sho+n that electrol*sis of a9ueous solutions of aluminum chloride and aluminum oxide dissolved in acid did not *ield metallic aluminum$ Havin. sho+n that an a9ueous s*stem +as useless for the (re(aration of aluminum b* electrol*sis% Hall turned his attention to the (ossibilit* of usin. +ater-free fused salts as solvents for aluminum oxide$(2) )ut first% he had to build a furnace ca(able of (roducin. and sustainin. hi.her tem(eratures than the coal-fired% bello+s-driven furnace that he had used in earlier ex(eriments$ <or this (ur(ose he ada(ted a secondhand% .asoline-fired stove to heat the interior of a cla*-lined iron tube$(3) Des(ite the hi.h tem(erature in this furnace he +as unable to melt the first substance he tried% the mineral fluors(ar% +hich is calcium fluorite (m$($ 380 de.rees Celsius)$ He then s*nthesi?ed and tried (otassium fluoride (m$($ !#8 de.rees Celsius)% sodium fluoride (m$($ 2!! de.rees Celsius)% ma.nesium fluoride (m$($ 288 de.rees Celsius) and aluminum fluoride (sublimation (oint 22 de.rees Celsius)$ The (otassium and sodium fluorides melted in the furnace but did not dissolve useful amounts of aluminum oxide$ He +as unable to fuse ma.nesium fluoride or aluminum fluoride$ Hall moved on to ex(eriments +ith the double fluoride of sodium and aluminum% +hich +as formulated 35a<$Al<3 in his da* and +as ,no+n as the mineral cr*olite$ He ,ne+ that this material +as available from natural sources$ 5o doubt he also ,ne+ that

mixtures of salts commonl* had lo+er meltin. (oints than the hi.her meltin. of the t+o$ Toda*% this substance is +ritten +ith a formula of 5a3Al<8$ 3t is understood to be an ionic com(ound containin. sodium ions and hexafluoroaluminate ions% Al<83-$ Hall s*nthesi?ed his cr*olite$ He also had to (re(are aluminum oxide$ He did so from alum% &Al(SO#)2$ 2H2O% +hich +as a common household substance in his da*$ He dissolved alum in +ater% (reci(itated aluminum h*droxide b* addin. +ashin. soda (5a2CO3)% another common household substance% filtered off the h*droxide% and dried it$ Hall1s older sister% 'ulia Hall% +ho had studied chemistr* in colle.e% follo+ed the ex(eriments closel* and (robabl* hel(ed (re(are some of the aluminum oxide$ He melted cr*olite (m$($ 000 de.rees Celsius) in the furnace and 9uic,l* found that it +as a .ood solvent for aluminum oxide$ He did this si.nal ex(eriment on <ebruar* 2% !!8 and re(eated it for his sister to see +hen she returned the next da* from a visit to Cleveland$ To do electrol*sis in the !!01s most (eo(le had to ma,e batteries$ Hall and 'e+ett made cells of ?inc in dilute sulfuric acid and .ra(hite in concentrated nitric acid$ (Such cells% ,no+n as )unsen batteries or )unsen-7rove cells% +ere commonl* used in electrol*sis ex(eriments before the advent of motor .enerators$) <or Hall1s ex(eriments this +as a lar.e underta,in.$ Due in (art to inefficiencies in the (rocess% about " moles of ?inc metal (H300 .) +ould be consumed in ma,in. one mole (H30 .) of aluminum metal$ Thou.h a .ood source of hi.h current% the )unsen batter* emits noxious fumes of nitro.en oxides$(#) Hall1s first attem(ts to (re(are aluminum metal b* electrol*sis +ere carried out on <ebruar* 8% !!8$ He used .ra(hite-rod electrodes di((in. into a solution of aluminum oxide in molten cr*olite held in a cla* crucible$ )ecause he observed .as formation around the (ositive electrode (anode)% Hall +as confident that electrol*sis +as occurrin.$ Ho+ever% +hen Charles cooled the melt and bro,e it o(en in 'ulia1s (resence% the* found onl* a .ra*ish de(osit on +hat had been the ne.ative .ra(hite electrode (cathode)$ He re(eated this ex(eriment several times over the next fe+ da*s$ <inall*% he reco.ni?ed that the ne+ material% +hich did not have the shin* metallic (ro(erties of aluminum% +as (robabl* silicon% +hich is a metalloid$ Sus(ectin. that this silicon had its ori.in in the silicates in the cla*% he decided to fabricate a .ra(hite crucible to use as a liner for the cla* crucible$ This .ra(hite crucible +as onl* 2 inches +ide and # inches dee($(") The first electrol*sis ex(eriment +ith this s*stem% in +hich he had added some aluminum fluoride to lo+er the meltin. (oint of cr*olite% +as (erformed on <ebruar* 23% !!8$ The electric current ran for several hours$ Fhen Charles cooled the melt and bro,e it o(en in 'ulia1s (resence% the* found several silver* buttons of aluminum$ As soon as (ossible% Charles too, the buttons to -rofessor 'e+ett% +ho confirmed that the* +ere aluminum$ 3f aluminum oxide brea,s% at least in (art% into ions in molten cr*olite% then the half reactions for the electrol*sis (rocess can be +ritten as6

At the anode% .ra(hite is consumed% and carbon dioxide is formed$ At the cathode% li9uid aluminum is formed$ The li9uid aluminum collects in the bottom of the crucible$ 3n the full* develo(ed method the heat to maintain the cr*olite in the molten state is .enerated b* the electrical resistance of the electrol*te$

The cr*olite solvent that Hall found for his (rocess has some fortunate (ro(erties in addition to bein. a solvent for aluminum oxide$ )ein. ionic% cr*olite is a .ood conductor of electricit*$ Althou.h the densit* of solid cr*olite is .reater than the densit* of solid aluminum at room tem(erature% the densit* of molten aluminum is .reater than that of molten cr*olite at the electrol*sis tem(erature$ As a conse9uence% li9uid aluminum metal collects in the bottom of the electrol*sis vessel +here the aluminum is (rotected from bein. reoxidi?ed b* ox*.en in the atmos(here$ -rofessor 'e+ett (la*ed a crucial role as Hall1s mentor$ <or his da* 'e+ett +as exce(tionall* +ell educated in chemistr* and exce(tionall* +ell travelled$ He had received an under.raduate de.ree from Iale in !A0 and had returned to Iale for .raduate +or, in chemistr* at the Sheffield Scientific School$ He then studied at 7Jttin.en in 7erman*% as +as essential for the best trainin. in science at the time$ There he met <riedrich FJhler% one of the t+o scientists first to isolate aluminum metal in the !201s$ <rom FJhler% 'e+ett learned directl* about aluminum and +as stimulated to obtain a small sam(le of this metal$ 'e+ett returned to the 4$S$ to +or, for a *ear as a (rivate assistant to Folcott 7ibbs at Harvard$ Then% after nomination b* the (resident of Iale% he tau.ht chemistr* for four *ears ( !A8- !!0) at the 3m(erial 4niversit* of To,*o% 'a(an$ He assumed the (osition of -rofessor of Chemistr* and ;ineralo.* at Oberlin in !!0$ Hall entered Oberlin Colle.e in !!0 and met 'e+ett durin. that first fall +hen he +ent to the laborator* in Cabinet Hall to bu* some .lass a((aratus and chemicals$ Durin. the *ear 'e+ett and Hall tal,ed about Hall1s interest in develo(in. a ne+ (rocess for extractin. aluminum$ Hall did not ta,e a formal course in chemistr* until his :unior *ear ( !!2-!3)% the standard time for such stud* in the !!0s$ He +as not on the rolls of the colle.e for the !!3-!# *ear and ma* have s(ent much of that *ear +or,in. in 'e+ett1s laborator* or his o+n home laborator*$ 3n the chemistr* class Hall heard 'e+ett1s tal, about aluminum and the challen.e to find an economical method for (re(arin. this element$ 'e+ett said% BAn* (erson +ho discovers a (rocess b* +hich aluminum can be made on a commercial scale +ill bless humanit* and ma,e a fortune for himself$B Hall said to some fello+ students% B31m .oin. for that metal$B 5ot onl* did 'e+ett challen.e Hall% but he also su((lied laborator* s(ace% materials% and u(-to-date chemical ,no+led.e$ <rom his ex(erience in mineralo.* 'e+ett ma* have (rovided the crucial idea of usin. cr*olite% as one +riter has su..ested$ Hall +as as ade(t in overcomin. the obstacles to the commerciali?ation of his ne+ electrol*tic (rocess as he +as in discoverin. it$ Fithin three *ears he and his (artners +ere ma,in. aluminum metal in 9uantit* at the ne+l* formed -ittsbur.h =eduction Com(an*% the (redecessor of Alcoa$ )ut first% Hall had to survive the defection of t+o )oston bac,ers +hom his brother had found and the attem(t b* the Co+les Clectric Smeltin. and Aluminum Com(an* to su((ress his ne+ (rocess b* bu*in. him out$ He also had to +ithstand a challen.e to his (atent ri.hts b* the <renchman -aul HKroult +ho had filed for a (atent for a similar electrol*tic (rocess usin. cr*olite in A(ril !!8$ (8) A .rou( or.ani?ed b* Ca(tain Alfred Hunt in -ittsbur.h (rovided the necessar* and (atient financial bac,in. for Hall +hile he brou.ht his (rocess from the laborator* scale to the commercial scale$ The Co+les Co$ made one further effort to infrin.e on Hall1s (atents +hich had to be fou.ht in court$ )ut% soon this remar,able ne+ metal +as bein. made faster than mar,ets for its use could be develo(ed$

A recreation of the Hall +oodshed is associated +ith the 'e+ett house$ This house is (art of the Oberlin Historical Societ* site on -rofessor Street :ust south of the Conservator*$ A lecture-demonstration recreatin. Hall1s ori.inal laborator* (rocess +as held in Oberlin in 2!8 on the centennial of the discover*$ <ootnotes6 $ =eaction of heav* oil LH(CH2)nM and 5a2CO3 at tem(eratures above the boilin. (oint of sodium metal% !22 de.rees Celsius$ 2$ Hall ,ne+ that 7raet?el had (re(ared ma.nesium metal b* electrol*sis of fused ma.nesium chloride$ (Scientific American% fall !!"$) 3$ 7asoline +as available in the Cleveland area because '$ D$ =oc,efeller +as in the earl* *ears of develo(in. Standard Oil there$ #$ 'ules Derne e9ui((ed the 5autilus +ith )unsen batteries in B20%000 /ea.ues 4nder the Sea$B Ca(tain 5emo and his cre+ must have had leather-lined lun.s$ "$ )ecause )rush Clectric +as develo(in. carbon arcs for street li.htin. in Cleveland% Hall (robabl* obtained his lar.e .ra(hite rod rather easil*$ 8$ HKroult +as the same a.e as Hall$ He had the advanta.e of a motor .enerator to su((ort his ex(eriments in usin. lar.e electric currents to do metallur.*$ HKroult did not (ursue the scale-u( and commerciali?ation of the aluminum-ma,in. (rocess in Curo(e until Hall had done so in the 4$ S$ =eferences6 5$ C$ Crai.% BCharles ;artin Hall - The Ioun. ;an% His ;entor% and His ;etal%B Journal of Chemical Education% 63% ""A ( 2!8)$ '$ Cd+ards% The 3mmortal Foodshed% Dodd% ;ead% and Co$% 5e+ Ior,% 2""$ H$ 5$ Holmes% B<ift* Iears of 3ndustrial Aluminum%B The )ulletin of Oberlin Colle.e% 5o$ 3#8% Au.$ 23A$ <$ <$ 'e+ett and <rances 7ulic, 'e+ett% BThe Chemical De(artment of Oberlin Colle.e from !33 to 2 2%B Chemistr* Su((lement% The Oberlin Alumni ;a.a?ine% Dol$ ND333$ 'ul* 222$ Written by Norman C. Craig (1992)

5orman Crai. standin. next to the aluminum statue of Charles ;artin Hall located in the &etterin. Hall of Science$ =eturn to the Oberlin Chemistr* De(artment Home -a.e$

($te! 'ea!)h

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6 P!%D"CT'%( 6 REFINING

Alumina Refining

$')T%!* P!%D"CT'%( &(+'!%(M&(T APP#'CAT'%() )TAT')T'C) (&,) 'A'

Overvie+ )auxite ;inin.

Alumina Refining

&n-uiries #in.s )ite Map

The aluminium industr* relies on the )a*er (rocess to (roduce alumina from bauxite$ 3t remains the most economic means of obtainin. alumina% +hich in turn is vital for the (roduction of aluminium metal - some t+o tonnes of alumina are re9uired to (roduce on tonne of aluminium$

The Bayer Process )a*er -rocess Chemistr* Smeltin. -rocessin. =ec*clin. ;a(s

The (rimar* aluminium industr* is de(endent on a re.ular su((l* of alumina for four functions6
1. Basic raw material for aluminiu m productio n Thermal insulator for the top of electrolyti c cells Coating

1.8 million tonne alumina refinery at Gove, orthern Territory, !ustralia

2.

3.