Aluminum Oxide 1

Aluminum Oxide
L. Keith Hudson, Aluminum Company of America, Alcoa Center, Pennsylvania 15069, USA

Chanakya Misra, Aluminum Company of America, Alcoa Center, Pennsylvania 15069, United States

Anthony J. Perrotta, Aluminum Company of America, Alcoa Center, Pennsylvania 15069, USA

Karl Wefers, Aluminum Company of America, Alcoa Center, Pennsylvania 15069, USA

F. S. Williams, Aluminum Company of America, Alcoa Center, Pennsylvania 15069, USA

1. General Aspects . . . . . . . . . . . . 1 3.1.8. Evaporation . . . . . . . . . . . . . . . 26

1.1. Aluminum Hydroxides . . . . . . . 2 3.1.9. Residue Disposal . . . . . . . . . . . . 27
1.2. Aluminum Oxide Hydroxides . . . 3 3.1.10. Energy in the Process . . . . . . . . . 28
1.3. Aluminum Oxide, Corundum . . . 4 3.2. Economic Aspects . . . . . . . . . . . 29
1.4. The Al2 O3 – H2 O System . . . . . . 4 4. Other Processes for Alumina Pro-
1.5. Thermal Decomposition of Alu- duction . . . . . . . . . . . . . . . . . . 29
minum Hydroxides . . . . . . . . . . 5 4.1. Raw Materials . . . . . . . . . . . . . 29
1.6. Aluminates and Related Com- 4.2. Alkaline Processes . . . . . . . . . . . 30
pounds . . . . . . . . . . . . . . . . . . 7 4.3. Acid Processes . . . . . . . . . . . . . 31
2. Bauxite, the Principal Raw Mate- 5. Metallurgical Alumina . . . . . . . . 32
rial . . . . . . . . . . . . . . . . . . . . . 7 5.1. Alumina Properties Required for
2.1. Definition and Geology . . . . . . . 7 Smelting . . . . . . . . . . . . . . . . . 32
2.2. Composition and Properties . . . . 7 5.2. Typical Specifications for Metallur-
2.3. Genesis of Bauxites . . . . . . . . . . 9 gical Alumina . . . . . . . . . . . . . . 33
2.4. Major Bauxite Deposits . . . . . . . 10 6. Industrial Alumina Chemicals . . 33
2.5. Economic Aspects . . . . . . . . . . . 11 6.1. Aluminum Hydroxides . . . . . . . 33
3. Bayer Process . . . . . . . . . . . . . . 11 6.2. Adsorbent and Catalytic Aluminas 34
3.1. History and Procedure . . . . . . . . 11 6.2.1. Preparation of Activated Aluminas . 34
3.1.1. Bauxite Preparation . . . . . . . . . . 12 6.2.2. Adsorbent Applications . . . . . . . . 36
3.1.2. Digestion . . . . . . . . . . . . . . . . . 13 6.2.3. Catalytic Applications . . . . . . . . . 37
3.1.3. Equipment . . . . . . . . . . . . . . . . 15 7. Ceramic Uses of Alumina . . . . . . 38
3.1.4. Residue Separation . . . . . . . . . . . 17 7.1. Calcined Alumina . . . . . . . . . . . 39
3.1.5. Precipitation . . . . . . . . . . . . . . . 20 7.2. Fused Alumina . . . . . . . . . . . . . 39
3.1.6. Impurities . . . . . . . . . . . . . . . . . 23 8. Toxicology and Industrial Hygiene 39
3.1.7. Calcination . . . . . . . . . . . . . . . . 25 9. References . . . . . . . . . . . . . . . . 39

1. General Aspects oxide of a then-undiscovered element. By the

1700s the earthy base alumina was recognized
Almost 4000 years ago Egyptians and Baby- as the potential source of a metallic element.
lonians used aluminum compounds in various Greville (1798) described a mineral from
chemicals and medicines. Herodotus men- India that had the composition Al2 O3 and
tioned alum in the fifth century b.c. and Pliny named it corundum [1302-74-5], derived from
referred to “alumen,” now known as alum, as a the native name of this stone. Haüy (1801)
mordant to fix dyes to textiles around 80 a.d. called a mineral diaspore [14457-84-2] (from
In 1754 Marggraf showed that a distinct com- the Greek “diaspora” meaning dispersion) be-
pound existed in both alum and clays. In 1761 cause it decrepitated on heating. Its composi-
the French chemist Guyton de Morveau pro- tion, Al2 O3 · H2 O, was determined by Vaque-
posed the name “alumine” for the base in alum, lin in 1802. Gibbsite [14762-49-3], named after
identified in 1787 by Antoine Lavosier as the the American mineralogist G. Gibbs, was found

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a01 557
2 Aluminum Oxide

by Dewey in 1820; Torrey (1822) showed this to one another in the direction of the a axis. The
mineral to have the composition Al2 O3 · 3 H2 O. hexagonal symmetry of this lattice type (brucite
The name hydrargillite [14762-49-3] was given type) is lowered to monoclinic. Triclinic symme-
to a similar mineral found later in the Ural Moun- try was found in larger gibbsite single crystals
tains. Using the newly developed technique of from the Ural Mountains [17].
X-ray diffraction, Böhm and Niclassen [13] In bayerite the layers are arranged in approx-
identified a crystalline aluminum oxide hy- imately hexagonal close packing. Because of
droxide, Al2 O3 · H2 O, later named böhmite shorter distances between the layers, the den-
(boehmite). Böhm discovered a second type of sity is higher than in the case of gibbsite. The
trihydroxide, Al2 O3 · 3 H2 O, a year later. Fricke crystal class and space group of bayerite have
[14] suggested the name bayerite [20257-20-9] not yet been established clearly.
for this compound, believing it to be the prod- The individual layers of hydroxyl ion octahe-
uct of the Bayer process, which he later identi- dra in both the gibbsite and the bayerite struc-
fied as gibbsite. Only few occurrences of natural tures are linked to one another only through
bayerite have been reported [15]. van Nord- weak hydrogen bonds. Bayerite does not form
strand et al. [16] reported a third form of tri- large single crystals. The most commonly ob-
hydroxide, which was later named nordstrandite served growth forms are spindle- or hourglass-
[13840-05-6] in his honor. shaped somatoids. The long axis of these soma-
toids stands normal to the basal plane; i.e., the
somatoids consist of stacks of Al(OH)3 layers
1.1. Aluminum Hydroxides (Fig. 2). The effect of alkali ions on the structures
of Al(OH)3 types was investigated by several
A general classification of the various modifica- workers [3], [18], [19]. Intercalation of Li+ ions
tions of aluminum hydroxides is shown in Fig- transforms gibbsite to the hydrotalcite structure
ure 1. The best defined crystalline forms are the [20].
three trihydroxides, Al(OH)3 : gibbsite, bayerite,
and nordstrandite, and two modifications of alu-
minum oxide hydroxide, AlO(OH): boehmite
and diaspore. Besides these well-defined crys-
talline phases, several other forms have been de-
scribed in the literature [2], [3]. However, there
is controversy as to whether they are truly new
phases or simply forms with distorted lattices
containing adsorbed or interlamellar water and
impurities.
Identification of the different hydroxides and
oxides is best carried out by X-ray diffraction
methods [3]. Mineralogical and structural data
are listed in Tables 1 and 2.
Figure 2. Somatoids of bayerite
Gelatinous hydroxides may consist of pre-
dominantly X-ray indifferent aluminum hydrox- Gibbsite crystals of appreciable size are not
ide or pseudoboehmite. The X-ray diffraction uncommon. Clear pseudohexagonal platelets
pattern of the latter shows broad bands that about 1 mm in diameter are known from Arö in
coincide with strong reflections of the well- Norway. Prismatic crystals 0.5 – 1 mm in length
crystallized oxide hydroxide boehmite. are occasionally produced in the Bayer process.
The aluminum hydroxides found abundantly Nordstrandite, the third form of Al(OH)3 ,
in nature are gibbsite, boehmite, and diaspore. was described by Van Nordstrand [16] and
Gibbsite and bayerite have similar structures. others [21]. The structures of nordstrandite and
Their lattices are built of layers of anion octahe- bayerite were investigated [22] and compared
dra in which aluminum occupies two thirds of with those of monoclinic and triclinic gibbsite,
the octahedral interstices. In the gibbsite struc- which had been determined previously [17].
ture, the layers are somewhat displaced relative
 Aluminum Oxide 3

Figure 1. Classification of aluminum hydroxides

(All figures courtesy of Aluminum Company of America)

Table 1. Mineralogic properties of oxides and hydroxides [3]

Phase Refractive index n20

D Cleavage Brittleness Mohs Luster

hardness
α β γ Average

Gibbsite 1.568 1.568 1.587 – (001) perfect tough 2.5 to 3.5 pearly vitreous

Bayerite – – – 1.583 – – – –

Boehmite 1.649 1.659 1.665 – (010) – 3.5 to 4 –

Diaspore 1.702 1.722 1.750 – (010) perfect brittle 6.5 to 7 brilliant pearly

ε ω Average

Corundum 1.7604 1.7686 – none tough when 9 pearly

compact adamantine

The lattice of nordstrandite is built of the 1.2. Aluminum Oxide Hydroxides

same, electrically neutral Al(OH)3 octahedral
layers that form the structural elements of gibb- Pseudoboehmite is formed during aging of X-
site and bayerite [14]. The lattice period amounts ray indifferent hydroxide gels as a precursor of
to 1.911 nm in the direction normal to the layer. trihydroxide. The reflections of pseudoboehmite
This corresponds to the sum of identical layer are broadened not only because of the very small
distances of bayerite plus gibbsite. The identi- particle size, but also because of variable dis-
cal nordstrandite structure consists of alternat- tances of the AlO(OH) double chains, which
ing double layers, in which the OH octahedra form the structural element of pseudoboehmite
are arranged once in the packing sequence of as well as of well-crystallized boehmite. The
bayerite, and then in that of gibbsite. Material lattice spacing in the direction of the c axis in-
containing continuous transitions from bayerite creases by 0.117 nm for each mole of excess wa-
through nordstrandite to gibbsite has been pre- ter [22].
pared through the proper selection of precipita- Boehmite consists of O, OH double lay-
tion conditions [18]. ers in which the anions are in cubic packing.
4 Aluminum Oxide
Table 2. Structural properties of oxides and hydroxides [3]

Phase Formula Crystal system Space Molecules Unit axis length, ×10−1 nm Angle Density,
group per unit cell g/cm3
a b c

Gibbsite Al(OH)3 monoclinic C 52h 4 8.68 5.07 9.72 94 ◦ 34  2.42

◦ 
Gibbsite Al(OH)3 triclinic – 16 17.33 10.08 9.73 94 10 –
92 ◦ 08 
90 ◦ 0

Bayerite Al(OH)3 monoclinic C 52h 2 5.06 8.67 4.71 90 ◦ 16  2.53

Nordstrandite Al(OH)3 triclinic C 1i 4 8.75 5.07 10.24 109 ◦ 20  –

97 ◦ 40 
88 ◦ 20 

Boehmite AlO(OH) orthorhombic D17

2h 2 2.868 12.227 3.700 – 3.01

Diaspore AlO(OH) orthorhombic D16

2h 2 4.396 9.426 2.844 – 3.44

Corundum Al2 O3 hexagonal (rhomb.) D63d 2 4.758 – 12.991 – 3.98

The aluminum ions are octahedrically coordi- alternating layers of Al and O ions. The corun-
nated. These layers are composed of chains of dum structure was determined in the early 1920s
[AlO(OH)]2 extending in the direction of the a [27]; numerous workers later confirmed and re-
axis [23]. The double layers are linked by hy- fined these data [3]. Properties of corundum are
drogen bonds between hydroxyl ions in adjacent listed in Tables 1 and 2.
planes. Boehmite crystals exhibit perfect cleav-
age parallel to the (010) plane.
In the diaspore structure the oxygen ions are 1.4. The Al2 O3 – H2 O System
nearly equivalent, each being joined to another
oxygen center through a hydrogen ion. The an- Under the equilibrium vapor pressure of wa-
ions are hexagonally close packed [24]. The po- ter, crystalline Al(OH)3 converts to AlO(OH)
sition of the hydrogen ion has been established at about 375 K. The conversion temperature ap-
by neutron diffraction [25]. The O – H – O dis- pears to be the same for all three forms of
tance is 0.265 nm. By infrared studies, the bond Al(OH)3 . At temperatures lower than 575 K,
energy for the hydrogen bridges in diaspore was boehmite is the prevailing AlO(OH) modifica-
determined to be 28.7 kJ/mol, compared with tion, unless diaspore seed is present. Sponta-
20.1 kJ/mol for boehmite [26]. neous nucleation of diaspore requires temper-
atures in excess of 575 K and pressures higher
than 20 MPa. In the older literature, therefore,
1.3. Aluminum Oxide, Corundum diaspore was considered the high-temperature
form of AlO(OH). The first reaction diagram of
The hexagonally closest packed α-Al2 O3 mod-
the phase transitions in the Al2 O3 – H2 O sys-
ification is the only stable oxide in the
tem was published in 1943 [28]. These workers
Al2 O3 – H2 O system. Corundum is a common
determined the gibbsite → boehmite conversion
mineral in igneous and metamorphic rocks. Red
temperature to be 428 K. Boehmite transformed
and blue varieties of gem quality are called ruby
to diaspore above 550 K; diaspore converted to
and sapphire, respectively. The lattice of corun-
corundum, α-Al2 O3 , at 725 K. Similar results
dum is composed of hexagonally closest packed
were reported in 1951 [29].
oxygen ions forming layers parallel to the (0001)
The system was reinvestigated in 1959 [30]
plane. Only two-thirds of the octahedral inter-
and in 1965 [31]. A phase diagram based on
stices are occupied by aluminum ions. The struc-
these data is shown in Figure 3. Diaspore is
ture may be described roughly as consisting of
 Aluminum Oxide 5

the stable modification of AlO(OH); boehmite The designation of the modifications of alu-
is considered metastable, although it is ki- minum hydroxides and oxides lacks unifor-
netically favored at lower temperatures and mity just as much as does the nomenclature of
pressures. This is because the nucleation en- the compounds. According to the general us-
ergy is lower for boehmite than for the con- age in crystallography, the most densely packed
siderably more dense diaspore. Nucleation is structures are designated as α-modifications [3].
additionally facilitated by the possibility that Bayerite, diaspore, and corundum fall within this
boehmite can grow epitaxially on Al(OH)3 . In class. The compounds with cubic packing se-
the Al2 O3 – Fe2 O3 – H2 O system, the presence quence, gibbsite and boehmite, have been des-
of the isostructural goethite, α-FeO(OH), low- ignated by the symbol γ. Nordstrandite can be
ers the nucleation energy for diaspore so that this classified as β-Al(OH)3 when regarding this
AlO(OH) modification crystallizes at tempera- compound not as an intergrowth of bayerite and
tures near 373 K [32]. This observation explains gibbsite, but as an independent modification.
the occurrence of diaspore in clays and bauxite
deposits that have never been subjected to high
temperatures or pressures. 1.5. Thermal Decomposition of
Aluminum Hydroxides
When aluminum hydroxides or oxide hydrox-
ides are heated in air at atmospheric pressure,
they undergo a series of compositional and struc-
tural changes before ultimately being converted
to α-Al2 O3 . These thermal transformations are
topotactic. Despite a loss of 34 or 15 % of mass
for the trihydroxides or oxide hydroxides, re-
spectively, the habit of the primary crystals and
crystal aggregates changes very little. This leads
to considerable internal porosity, which may in-
crease the specific surface area of the material to
several hundred m2 /g. Structural forms develop
that, although not thermodynamically stable, are
well reproducible and characteristic for a given
temperature range and starting material. These
transition aluminas have been the subject of nu-
merous investigations because of their surface
activity, sorptive capacity, and usefulness in het-
Figure 3. The Al2 O3 – H2 O system
Dashed lines [21], solid lines [22], [28] erogeneous catalysis. The literature in this field
of physical chemistry has been reviewed up to
1987 [3].
Nomenclature. Although there is fairly good The simplest transformation is that of dias-
agreement in the more recent literature on phase pore to corundum. As the structures of these
fields and structures of the crystalline phases in two compounds are very similar, the nucle-
the Al2 O3 – H2 O system, the nomenclature is ation of α-Al2 O3 requires only minor rear-
still rather unsystematic. rangement of the oxygen lattice after the hy-
Bayerite, gibbsite (hydrargillite), and nord- drogen bonds are broken. A temperature below
strandite are trihydroxides of aluminum, and 860 – 870 K is sufficient for complete conver-
not oxide hydrates. The designation “aluminum sion. The newly formed corundum grows epi-
oxide monohydrate” for boehmite and diaspore taxially on the decomposing diaspore, with the
is also incorrect. Both are true oxide hydrox- (0001) plane of Al2 O3 parallel to the (010) plane
ides. Molecular water has been determined only of AlO(OH) [33]. Transformation to corundum
in poorly crystallized, nonstoichiometric pseu- (α-Al2 O3 ) proceeds through an intermediate α’-
doboehmite. Al2 O3 phase [34].
6 Aluminum Oxide

in the formation of γ-AlO(OH). With increas-

ing loss of water, a large internal porosity devel-
ops. The lattice voids left by the escaping water
are not readily healed because of the slow diffu-
sion in this low temperature range. The voids are
oriented parallel and perpendicular to the basal
plane of the trihydroxide crystals (Fig. 4).
The highest surface area and lowest crys-
talline order of the solid (not counting newly
formed boehmite) is obtained at a temperature
around 675 K. With increasing temperature the
surface area decreases, while the density of the
solid shows progressively higher values (Fig. 5).
Figure 4. Gibbsite heated to 573 K
This trend is the result of progressive reordering
and consolidation of the solid.
During the thermally driven consolidation
and reordering, the solid goes through structural
stages that are influenced by the nature of the
starting material as well as by heating rates, fur-
nace atmosphere, and impurities. The general
reaction paths are illustrated in Figure 6, which
shows the various intermediate transition forms
that have been identified during the reordering
process.

Figure 6. Decomposition sequence of aluminum hydroxide

Transition oxides formed at lower tem-

Figure 5. Specific surface area, loss on ignition (LOI), and
density of heated Al(OH)3
peratures are mostly two-dimensional, short-
range ordered domains within the texture of
the decomposed hydroxides. Extensive three-
The thermal transformation, at ambient pres-
dimensional ordering begins at about 1050 K.
sure, of boehmite and the trihydroxides to
Until completely converted to corundum, the
α-Al2 O3 requires considerably more struc-
solid retains considerable amounts of OH− ions.
tural rearrangements and is generally not com-
Most likely protons are retained to maintain
pleted until the temperature reaches at least
electroneutrality in areas deficient of cations.
1375 – 1400 K. The first step in the reaction se-
Therefore, the presence of protons may retard
quence is the diffusion of protons to adjacent OH
the reordering of the cation sublattice. The high
groups and the subsequent formation of water
surface area (> 75 m2 /g) of γ-Al2 O3 has been
[35], [36]. This process begins at a temperature
shown to provide thermodynamic stability [37].
near 475 K. If this water cannot diffuse rapidly
Addition of fluorine to the furnace atmosphere
out of larger trihydroxide particles, hydrother-
removes protons. As a result, rapid transition
mal conditions may develop locally, resulting
to α-Al2 O3 occurs at temperatures as low as
 Aluminum Oxide 7

1150 K. Markedly tabular corundum crystals assumed to be a dihydrate of aluminum oxide,

form, possibly because the preceding transition bauxite was later recognized as being composed
alumina is mostly two-dimensionally ordered of aluminum hydroxide, iron oxide and hydrox-
[38]. ide, titanium dioxide, and aluminosilicate min-
Transition forms other than those shown in erals [2].
Figure 6 can be obtained by hydrothermal treat- Early in this century, major bauxite deposits
ment [3]. The structures of various transition were found in various parts of the Tertiary and
forms have been investigated [17], [22], [39]. Cretaceous limestone formations of the Euro-
pean Alps; also in several locations on the North
American continent, e.g., in Arkansas, Alabama,
1.6. Aluminates and Related and Georgia. Since the 1920s, extensive deposits
Compounds have been discovered in the tropical and subtrop-
ical climate belts.
Sodium oxide forms several compounds with The oldest known bauxites developed in the
aluminum oxide. These so-called β-aluminas Precambrian; the youngest are of recent ori-
represent a group of aluminates having the same, gin. Deposits may occur as extensive, flat bod-
or very similar, structures but variable chemical ies blanketing areas of many square miles; they
composition. Their molar ratios (Na2 O : Al2 O3 ) may form irregularly shaped fillings of dolinas
can vary between 1 : 1 and 1 : 11. The in old karst surfaces, or lenses several hundred
1 : 1 sodium aluminate, NaAlO2 [1302-42-7], meters in diameter and tens of meters thick.
exists in at least two allotropic modifica- Allochtonous, i.e., displaced bauxites, are also
tions. Orthorhombic β-NaAlO2 is stable be- common; erosion of primary deposits and rede-
low 750 K; the higher – temperature γ modifica- position of the detritus in valleys or along moun-
tion is tetragonal. For preparation and properties tain slopes has frequently led to mineable accu-
of technical sodium aluminate, → Aluminum mulations of ore.
Compounds, Inorganic, Chap. 2.1. Many of the geologically younger bauxites
The 1 : 11 β-Al2 O3 crystallizes from melts are covered only by thin layers of soil; others are
containing aluminum oxide and sodium oxide or buried by coastal or alluvial sediments. Older
other sodium compounds. A 1 : 5 β-alumina has deposits, especially in the Balkans or the Ural
been prepared by heating α-Al2 O3 with NaAlO2 Mountains, often are overlain by carbonate rocks
or Na2 CO3 at about 1325 K. hundreds of meters thick. Regardless of their ge-
Several other β-aluminas containing CaO, ologic age, all bauxites were formed during con-
BaO, or SrO in 1 : 6 ratio also have been re- tinental periods [40].
ported [3].
β-Alumina is of interest to its use as a solid
electrolyte in sodium – sulfur secondary batter- 2.2. Composition and Properties
ies ( → Batteries).
The chemical composition of bauxites of various
origin is given in Table 3 [2]. Aluminum oxide,
iron oxide, and titanium and silicon dioxides are
2. Bauxite, the Principal Raw the major chemical components of all bauxites.
Material Alkali and alkaline earth compounds are rarely
found.
2.1. Definition and Geology Gibbsite, γ-Al(OH)3 , is the predominant
aluminum mineral in the geologically young
The term bauxite [1318-16-7] is used for sed- bauxites of the tropical climate belt. Mesozoic
imentary rocks that contain economically re- and older bauxite contain mostly boehmite (γ-
coverable quantities of the aluminum minerals AlO(OH)) or diaspore (α-AlO(OH)). Since their
gibbsite, boehmite, and diaspore. The name de- formation, many of the older bauxites have been
rives from the description by Berthier, in 1821, buried under considerable layers of younger
of a sediment that occurred near the village of sediments and often were subjected to tectonic
Les Baux in the Provence, France. Originally stress. Boehmite and diaspore formation appears
8 Aluminum Oxide
Table 3. Principal chemical constituents of various bauxites, wt %

Country and location Al2 O3 SiO2 Fe2 O3 TiO2 Loss on ignition

Australia
Darling Range 37 26.5 16.4 1.1 19.3
Weipa 58 4.5 6.9 2.5 26.8

Brazil
Trombetas 52 5.1 13.9 1.2 28.1

France
Southern districts 57 4.6 22.6 2.9 15.1

Guyana
Mackenzie 59 4.9 2.9 2.4 30.4

Guinea
Friguia 49 6.1 14.2 1.6 28.1
Boke 56 1.5 7.9 3.7 30.1

Hungary
Halimba 52 6.6 23.5 2.9 18.1

India
Orissa 46 2.7 22.4 1.1 24.2

Indonesia
Bintan 53.5 3.9 12.1 1.6 29.2

Jamaica
Clarendon 47.8 2.6 17.6 2.3 27.3

Surinam
Onverdacht 59 4.3 3.1 2.5 30.9
Moengo 54 4.2 10.4 2.8 28.9

United States
Arkansas 51 11.2 6.6 2.2 28.4

Former Soviet Union

Severouralsk 54 6.2 14.8 2.4 15.7

Former Yugoslavia
Mostar 52 3.9 21.2 2.7 16.2

to be related to an increasing degree of meta- Goethite, α-FeO(OH) [1310-14-1], and

morphism. However, both minerals also occur hematite, α-Fe2 O3 [1309-37-1], are the most
in young deposits, although in minor quantities. prevalent iron minerals in bauxites. They are
The chemical environment obviously plays as practically inert under the conditions of the
important a role in the formation of boehmite Bayer process. In both materials, some of the
and diaspore as do pressure and stress [40]. iron may be replaced isomorphically by alu-
Dissolution of gibbsite requires the mildest minum ions. This amount of aluminum is in-
conditions in the Bayer process (see Sec- cluded in the chemical analysis of the bauxite
tion 3.1.2). Higher temperatures and alkali con- but is normally not extracted in the digest. Mag-
centrations are necessary for the digestion of netite (Fe3 O4 ) is found in some European baux-
boehmite and diaspore. Technically, both oxide ites; pyrite (FeS2 ) and siderite (FeCO3 ) also may
hydroxides can be processed without difficul- occur. Decomposition of pyrite may lead to high
ties. The abundance of high-grade gibbsitic sulfur levels in the process solutions.
bauxites, however, has made boehmite- and Anatase, TiO2 [1317-70-0], is the titanium
diaspore-rich ores economically less attractive. mineral found most frequently in bauxites. Ru-
tile, TiO2 [1317-80-2], occurs in some European
 Aluminum Oxide 9

deposits; FeTiO3 is also present in minor quan- 2.3. Genesis of Bauxites

tities, especially in titanium-rich bauxites. Tita-
nium dioxide minerals are attacked under only Many of the geologically young bauxite deposits
the most severe conditions of the Bayer process. are located in the savannah region, which ex-
Silicon dioxide may occur as quartz tends north and south of the tropical rain forest
[14808-60-7], as in the bauxites of the Darling belt. The climate of this region is characterized
Range in Western Australia. Most commonly, by a high mean annual temperature and abun-
however, SiO2 is associated with the clay min- dant precipitation during the rainy season. De-
erals kaolinite, halloysite, or montmorillonite. posits occur on gently sloping hills or on pene-
These aluminosilicates react with sodium alu- plains. The stratigraphic evidence shows that
minate solutions to form insoluble sodium alu- these bauxites have formed in situ. Parent rocks
minum silicates during digest, causing loss of may be coarse-grained, igneous rocks such as
sodium hydroxide and extractable alumina. The syenite, phonolite, basalt, or gabbro. However,
amount of so-called reactive silica is one of the large deposits also developed on kaolinitic sand-
major factors determining quality and price of stones, on phyllites, and on schists. A layer of
the ore. kaolinitic clay is frequently found between the
Minor constituents, such as chromium, vana- ore body and the parent rock.
dium, zinc, and gallium, have little effect on the Bauxite probably forms during long peri-
Bayer process or on the quality of the final prod- ods of low geologic activity when the combi-
uct. Some tend to accumulate in the recirculated nation of high temperature, abundant precipita-
process solutions (e.g., gallium and vanadium) tion, and good vertical drainage favors intensive
and must be removed periodically by appropri- chemical weathering. The sequence of leach-
ate treatments. ing begins with removal of alkali followed by
The physical properties of bauxites, i.e., tex- the removal of alkaline earths. Oxides of iron,
ture, hardness, and density, can vary widely. aluminum, titanium, and silicon are mobilized
Geologically old diaspore bauxites, especially and reprecipitated as hydroxides and oxides.
those high in iron oxide, are very hard and can Aluminum hydroxide and silica form kaolinite,
reach densities of 3.6 g/cm3 . Young tropical de- Al4 (OH)8 Si4 O10 . This sequence first leads to
posits, in contrast, may have an earthy, soft tex- the formation of tropical soils (laterites). Baux-
ture and a density around 2.0 – 2.5 g/cm3 . Al- itization follows when the climatic, chemical,
lochtonous bauxite often consists of hard nod- and topographic conditions prevail long enough
ules embedded in a soft, usually clayey matrix. to allow the removal of silicon dioxide as well.
Porous textures also occur. The color of baux- The bauxite deposits of the Mediterranean
ites is largely determined by the type and par- region, the Caribbean Islands, and many other
ticle size of the prevalent iron mineral. Highly locations that are associated with tertiary and
dispersed goethite tends to be yellow to orange, older limestone formations (karst bauxites) were
whereas dark brown tones usually are associated formed by a similar weathering process. Par-
with coarser hematite. Colors can vary greatly ent materials were lateritic soils and clays trans-
within a single ore body. ported into the karst region and deposited in de-
Hardness, texture, and the amount of overbur- pressions. During extended terrestrial periods,
den determine the methods applied for bauxite high mean temperatures, copious precipitation,
mining. Deposits in Greece, former Yugoslavia, and good vertical draining through the porous
Hungary, and the former Soviet Union require limestone bedrock facilitated a thorough desilifi-
deep mining to depths of several hundred meters, cation. In the older literature, the parent material
often complicated by the difficulties of control- for karst bauxitization was reported to be clayey
ling water levels in the porous limestone forma- residue left after weathering of substantial lay-
tions. Tropical bauxites frequently are located so ers of carbonate rocks [41]. Researchers have
close to the surface that they can be recovered shown conclusively that igneous rocks were the
with normal earth-moving equipment. source of this material [42–44].
Comprehensive reviews on the geology, min-
eralogy, and genesis of bauxites have been pub-
lished [40], [45].
10 Aluminum Oxide
Table 4. World bauxite reserves and production, 103 t [46]

Country Mine production Reserves

1996 1997

United States n.a. n.a. 40 000

Australia 43 100 43 500 7 900 000
Brazil 9700 9700 2 900 000
China 6 200 7000 2 000 000
Guinea 14 000 14 000 900 000
Guyana 2000 2000 900 000
India 5100 5500 200 000
Jamaica 11 829 12 000 2 000 000
Russia 3300 3300 200 000
Surinam 4000 4000 600 000
Venezuela 5600 5600 350 000
Other countries 8928 8900 4 400 000
World total (rounded) 114 000 115 000 28 000 000

2.4. Major Bauxite Deposits South America. On the outer slopes of the
old Guyana Shield, many economically impor-
Until the 1950s, the European aluminum indus- tant deposits have been found. They are lo-
try was supplied from the karst bauxite deposits cated in the Amazon Basin of Brazil, in Colom-
of France, Hungary, former Yugoslavia, and bia, Venezuela, Surinam, Guyana, and French
Greece. United States sources (Arkansas) and Guyana. Surinam and Guyana have been pro-
ore from Surinam provided the raw material for ducing for more than 60 years, whereas the
North American production. Since then, the pic- Brazilian Amazon deposits have been mined
ture has changed dramatically. The four largest only recently. Bauxite also is produced in the
bauxite producers of 1990, namely, Australia, Pocos de Caldas area in Southern Brazil, state
Guinea, Jamaica, and Brazil (Table 4), hardly of Minas Gerais. The South American bauxites
would have been mentioned in 1950. Today, generally are geologically young, gibbsitic ores.
they provide more than half of the world’s to- Caribbean. Jamaica and the Dominican Re-
tal bauxite output. public have major reserves of karst bauxites that
Africa. The Savannah region covers an area occur on Tertiary limestones under generally
of the African continent that has experienced low very thin overburden. Although gibbsite is the
geologic activity for a long time. In this belt, main aluminum mineral, some boehmite also is
which stretches from the Ivory Coast to Mada- present. Jamaica has been one of the world’s
gascar, very large bauxite deposits were found. leading bauxite producers for the past 20 years.
The major production is currently concentrated North America. The only economically im-
in Guinea and Ghana. Cameroon, Sierra Leone, portant deposit is located in Arkansas, where
Mali, and the Congo region, among other areas, gibbsitic bauxite developed on nepheline syenite
have substantial reserves. during the Eocene. Less than 5 × 107 t of bauxite
Australia. Major deposits are located in the remain, and the grade is declining.
Darling Range in Western Australia, on the Gove Europe. Except for a few commercially in-
Peninsula in the Northern Territory, and on the significant occurrences, all European bauxites
Cape York Peninsula in Queensland. Bauxite are of the karst type. The oldest deposits (De-
also occurs in New South Wales, in Victoria, vonian/Mississippian) are those of the Tikhvin
and on the island of Tasmania. The Australian area in the former Soviet Union; the youngest
deposits developed between the Eocene and are the Eocene bauxites of former Yugoslavia.
Pliocene epochs on substrates ranging from Pre- Most European deposits developed during the
cambrian sandstones to Tertiary basalts. Gibb- Lower and Upper Cretaceous, e.g., the diaspore
site is the predominant aluminum mineral, al- and boehmite bauxites of France, Greece, and
though some boehmite occurs in all but the West- Romania, and the gibbsite and boehmite baux-
ern Australian deposits. ites found in Hungary, former Yugoslavia, and
 Aluminum Oxide 11

Italy. Today, all European mines combined con- 3. Bayer Process

tribute only about 15 % of world production.
Asia. Major deposits of gibbsite bauxites oc- 3.1. History and Procedure
cur in India; the island of Kalimantan (In-
donesia) has large potential reserves. Numerous In 1855 the French mining engineer Louis le
bauxite deposits, most of them containing geo- Chatelier obtained alumina from bauxite by
logically old, diaspore-rich ore, were found in sintering with sodium carbonate at 1200 ◦ C and
China. Substantial deposits also are located in leaching the sodium aluminate with water. Alu-
Western Siberia. minum hydroxide was then precipitated from the
sodium aluminate solution by carbon dioxide.
Early use of aluminum hydroxide was chiefly as
2.5. Economic Aspects a mordant in the textile dyeing industry. The de-
mand for pure alumina increased rapidly when
The proved reserves of bauxite shown in Table 4 it became the raw material for aluminum pro-
are sufficient to supply the world aluminum in- duction upon development of the Hall – Héroult
dustry for a few centuries. Total resources are cell. The Austrian chemist Karl Josef Bayer
estimated by the U.S. Geological Survey at 55 received German patent 43977 in August, 1888
to 75 × 109 t. Because of the worldwide dis- for a new, improved process for production of
tribution of significant ore deposits, a disrup- aluminum hydroxide from bauxite, and the pro-
tion of bauxite supply for political reasons ap- cess became known as the Bayer process in his
pears highly unlikely. In 1974 several major honor. Bayer initially worked on his process at
bauxite-producing nations formed the Interna- the Tentelev chemical plant near St. Petersburg
tional Bauxite Association (IBA) with the in- in Russia. Between 1888 and 1900 he supervised
tent of increasing control over the exploitation the construction of Bayer process plants in Ger-
of their bauxite deposits. Although levies were many, England, France, Italy, and the United
increased substantially, competition from coun- States. The Merrimac Chemical Company in
tries not associated with the IBA helped maintain
a reasonable price structure. Table 5. World alumina production, 103 t Source: Roskill’s Metals
Dissolution of gibbsite requires the mildest Databook 1997
conditions in the Bayer process (see Sec- Country Production
tion 3.1.2). Higher temperatures and alkali con-
centrations are necessary for the digestion of 1996 1997
boehmite and diaspore. Technically, both oxide Australia 13 008 13 349
hydroxides can be processed without difficulty. Brazil 2 147 2 800
Canada 1 064 1 100
The abundance of high-grade gibbsitic bauxites, China 2 080 n.a.
however, has made boehmite- and diaspore-rich France 425 430
ores economically less attractive. Germany 994 1 000
Greece 630 630
Economic and political considerations favor Guinea 630 622
refining of bauxite near the deposit and shipment Hungary 353 n.a.
India 1 650 1 660
of either alumina or aluminum ingot. Brazil, Ireland 1 186 1 300
Surinam, and Australia have smelters, although Italy 857 880
their refining capacity by far exceeds the de- Jamaica 3 030 3 200
Japan 743 750
mands of domestic metal production. Jamaica Spain 1 095 1 100
and Guinea refine a substantial portion of their Surinam 1 579 1 600
Turkey 172 170
own bauxite production. United Kingdom 110 110
About 25 % of all bauxite mined is used for United States 4 530 4 780
producing refractories, abrasives, catalysts, ad- Venezuela 1 641 1 700
Yugoslavia 150 300
sorbents, and other industrial chemicals. World total 43 600 45 000
12 Aluminum Oxide

Massachusetts first used the Bayer process in the thereby reversing the reaction that previously
United States, and the Alcoa plant in East St. had taken place in the digester. Again, the heat
Louis, Illinois, was constructed in 1901. Since removed in cooling the solution is used to heat
then, plants have been built in more than 25 a colder stream in the process. After the pre-
countries, and the present world alumina capac- cipitation reaction has proceeded to the point
ity is over 40 × 106 t/a (Table 5). that about half of the Al2 O3 in the solution has
The important features exploited in the Bayer been removed, the mixture of solids and solu-
process are that boehmite, gibbsite, and diaspore tion is sent to classifiers. The fine Al(OH)3 par-
can be dissolved in NaOH solutions under mod- ticles are returned to the process to serve as seed.
erate hydrothermal conditions; the solubility of The coarse particles are washed and calcined to
Al2 O3 in NaOH is temperature dependent; most Al2 O3 . Excess solution introduced in washing
other components of the bauxite are quite inert in the product and the residue must be removed by
the process; and the silica that does dissolve sub- evaporation. In some cases the solution is treated
sequently forms a nearly insoluble compound. to remove both organic and inorganic impurities
These features permit formation of a sodium alu- before the solution is recycled through the plant.
minate solution, physical separation of the im-
purities, and precipitation of pure Al(OH)3 from
the cooled solution. 3.1.1. Bauxite Preparation
The main features of the Bayer process have
remained unchanged for the last 100 years, al- The bauxite entering the refinery must be uni-
though the scale of operations has been enlarged form and sufficiently fine that extraction of the
considerably due to chemical engineering devel- Al2 O3 and the other operations are successful.
opments. Figure 7 shows the flow sheet of the The chemical composition of bauxite varies.
process as it is now practiced. Uniformity is improved by blending material
Each operation in the process is carried out mined from several pits and, if necessary, by
in a variety of ways. The process begins with adding bauxite from storage piles. Ground baux-
preparation of the bauxite by blending for uni- ite cam be stpred as a slurry in surge tanks be-
form composition followed by grinding. In most fore it is pumped to digestion. These agitated
plants the bauxite is ground while suspended in tanks are operated so that plant feed is uniformly
a portion of the process solution. This slurry is blended for several hours. Sometimes bauxites
mixed with the balance of the heated NaOH so- are dried to improve handling or washed to re-
lution, then treated in a digester vessel at well move clay.
above atmospheric pressure. The digest reaction Hard bauxite is reduced to particles finer than
is: 2 cm in roll or cone crushers and hammermills.
Before it enters the process it is ground further
Al(OH)3 + Na+ + OH− −→ Na+ + Al(OH)−
4
to less than 0.15 cm.
Previously, fine grinding was done in dry
Additional reactions convert impurities such mills operating in closed circuit with vibrating
as SiO2 , P2 O5 , and CO2 to relatively insoluble screens. Such operation required very dry baux-
compounds. The slurry leaves the digester at a ite to avoid blinding the screens. This resulted in
temperature above its atmospheric boiling point a dusty working environment. In most modern
and is cooled by flashing off steam as the pres- plants, the bauxite is mixed with a portion of the
sure is reduced in several stages. The flashed process solution and is ground as a slurry. Rod
steam is used to heat the slurry and the solu- mills and ball mills are used most frequently.
tion going to the digester. The bauxite residue The ground slurry may be passed over screens
solids are separated from the sodium alumi- or through cyclones, with the fine particles pro-
nate solution in two steps so that the coarse gressing and the coarse ones being returned to
fraction is processed separately from the fine. the mills.
Both residue fractions are washed and discarded. In all-wet grinding the bauxite feed and the
The solution, being free of solids, is cooled and flow of solution are controlled to keep the solids
seeded with fine crystals of Al(OH)3 ; this causes content of the slurry between 45 and 55 %. The
the Al(OH)− 4 ions to decompose to Al(OH)3 , power consumed by the mill drive is an indicator
 Aluminum Oxide 13

Figure 7. Bayer process flow sheet

of the amount of grinding being done and may be available Al2 O3 is present as gibbsite, boehmite,
used to control the feed to the mill. On a longer diaspore, or a mixture of these minerals. The
time scale the particle size of the product can be dissolution rates of the three are quite differ-
used to make changes in the grinding operation. ent. Generally, if the bauxite contains mixed
phases, the digestion conditions will be chosen
on the basis of the least soluble compound. Any
3.1.2. Digestion Al(OH)3 or AlOOH left undissolved can act as
seed in the clarification step, causing precipi-
In digestion, all of the Al2 O3 in the bauxite must tation of Al(OH)3 while the residue is still in
be extracted. A solution is produced that con- contact with the solution. In the sweetening pro-
tains the maximum Al2 O3 concentration that cess, boehmitic bauxite is digested under rela-
can remain stable through the rest of the pro- tively mild conditions, producing an interme-
cess. This must be accomplished while using a diate Al2 O3 concentration. In a separate ves-
minimum amount of energy. sel, gibbsitic bauxite is added to the flow from
The conditions for digestion can and do vary the first digest to raise the Al2 O3 concentra-
widely. The first consideration is whether the tion to the desired level. Another approach is
14 Aluminum Oxide

to digest only the gibbsite in a mixed bauxite. NaOH concentration, or both [1–4]. As a re-
The residue is separated from the solution and sult, operating conditions in plants vary widely.
redigested under more severe conditions to re- Higher digest temperatures result in higher pres-
cover the boehmite. This method reduces the sures, making the equipment more expensive.
flow to the high-temperature digest and so re- There also is the need for more heat-exchange
quires lower capital and operating costs. equipment, which further increases capital costs.
High concentrations, on the other hand, permit
increased production from a given flow rate and,
hence, from a given plant installation. Precipita-
tion is thought to occur better at lower concentra-
tions, but use of low precipitation concentrations
while digesting at high concentrations requires
dilution and additional operating costs for subse-
quent evaporation. Choosing digester conditions
involves balancing these physical factors with
local economics, together with the designer’s ex-
perience. This has resulted in the spectrum of
operating conditions given in Table 6.
The conditions listed in the first line of Ta-
ble 6 are those for digesting bauxite at the at-
mospheric boiling point. Quite high alkali con-
centrations are required and the evaporation re-
quirement is an extraordinary 5.3 t of water for a
tonne of Al2 O3 . Most plants digesting gibbsitic
bauxite use the conditions on the second line of
Table 6. Boehmitic bauxite is digested using one
of two general sets of conditions. The first is Eu-
ropean practice, in which higher concentrations
and dilution prior to precipitation are preferred
to higher digest temperatures. When American
companies began processing boehmitic bauxite
from the Caribbean area, most chose the same
concentrations used for gibbsitic bauxite; there-
fore, a higher temperature was required.
The second important reaction in digestion is
desilication. In the equation below, kaolinite is
used to illustrate the reaction of siliceous min-
erals with the process solution:
Al2 O3 · 2 SiO2 · 2 H2 O + 6 NaOH
→ 2 NaAlO2 + 2 Na2 SiO3 + 5 H2 O
The soluble products react to form a
series of precipitates with zeolite struc-
ture, having a composition of approximately
Na8 Al6 Si6 O24 (OH)2 .
Depending on temperature and concentra-
Figure 8. Phase diagram Na2 O–Al2 O3 –H2 O
tion, the ratio of Al2 O3 :×SiO2 in the zeolite
(tectosilicate) structure can vary. For each Al3+
The solubility data (Fig. 8) show that the replacing Si4+ in the lattice, one Na+ is taken
Al2 O3 concentration in the process solution can up to maintain charge neutrality. Anions, such as
be increased by increasing the temperature, the SO2− 2−
4 or CO3 may substitute for OH in the
−

structure. The formation of the zeolitic desilica-

 Aluminum Oxide 15
Table 6. Commercial digestion conditions

Bauxite type Temperature, K cNaOH , g/L Final cAl2 O3 , g/L

gibbsitic 380 260 165

415 105 – 145 90 – 130

boehmitic 470 150 – 250 120 – 160

510 105 – 145 90 – 130

diaspore ∗ 535 150 – 250 100 – 150

∗ CaO is added to digests to accelerate dissolution of diaspore.

tion product (DSP) therefore leads to costly loss that the sodium required by the process was sup-
of sodium hydroxide. This reaction, however, plied more cheaply as Na2 CO3 . Its current im-
is necessary for lowering the level of dissolved portance is in control of the CO2−
3 concentration,
SiO2 to less than 0.6 g/L, the maximum accept- which, at high levels, can affect precipitation.
able concentration. In modern practice, the causticization reaction
The rate-determining step in the desilication is carried out on dilute process solutions outside
reaction is the nucleation and crystallization of the digester. Maintaining low concentrations and
the desilication product. Therefore, the presence having much of the NaOH combined as NaAlO2
of seed particles is important; without seeds, so- are favorable to more complete reaction of CO2− 3
lutions containing 0.75 g/L SiO2 will not react with Ca2+ .
in 40 min at 415 K. This has led to the paradoxi-
cal situation that some bauxites contain too little
reactive SiO2 for good desilication. The slurry 3.1.3. Equipment
blending and storage operation discussed earlier
can be an important part of the desilication pro- The equipment for digestion includes the reactor
cess. If the storage temperature is above 355 K, vessel, heat-exchange equipment, and pumps.
about 80 % of the reaction takes place in 8 h. The first reactors were horizontal vessels with
More important, seed is formed so the desilica- crude agitators mounted on axial shafts. These
tion reaction in the digest is not delayed. Very were filled with a slurry of bauxite, lime, and
low SiO2 concentrations can be achieved if an process solution. They were closed and heated
excess of CaO is charged. At high temperatures, individually by injecting high-pressure steam.
and with the lime additions, a less soluble desil- At the end of the designated holding time, a
ication compound (cancrinite) is formed. Euro- discharge valve was opened and a slurry was
pean plants use longer holding times during or forced into another vessel at atmospheric pres-
after digestion to facilitate desilication. sure. Only a small portion of the steam flash-
Some CaO is added to the digest even when ing from the slurry as the pressure was reduced
extreme desilication is not required. The calcium could be recovered. Continuous operation was
reacts with the carbonate and phosphate com- introduced in the 1930s in which heat could be
pounds as follows: exchanged between the hot stream leaving the
digester and the cooler, incoming stream. This
CaO + H2 O → Ca(OH)2 greatly reduces the energy requirements.

Ca(OH)2 + Na2 CO3 → CaCO3 + 2 NaOH (causticization) Reactors. Digester vessels, whether batch or
continuous, provide intimate contact between
5 Ca(OH)2 + 3 Na3 PO4 → Ca5 (PO4 )3 OH + 9 NaOH the bauxite and the solution for a period long
enough to complete the extraction and desili-
The last reaction controls the level of phosphates cation processes. The equipment designed for
in the process solution; this impurity can affect this purpose is quite diverse. Agitated horizon-
clarification adversely. Causticization in the di- tal vessels have been replaced by vertical units
gest was more important when prices were such to avoid the mechanical problems with sealing
16 Aluminum Oxide

Figure 9. High-temperature digestion and heat recovery

the agitator shaft. Both designs have used a se- centrations involved, there may be stress cor-
ries of vessels to minimize short circuiting of rosion cracking resulting from alkali embrittle-
the flow. European practice includes use of a se- ment. The presence of the [Al(OH)4 ]− ions re-
ries of vertical agitated vessels, each operating duces the activity of OH− in the solution. Finely
at a higher temperature than the preceding one. divided Fe2 O3 in the bauxite quickly saturates
These units are heated by flashed steam in inter- the solution with Fe3+ , suppressing corrosion of
nal steam coils. A German digester design uses the metal. Some digestion equipment has been
concentric pipes; the liquid being heated flows nickel plated for safety.
through the inner pipe while the hot slurry from Flashing. In most plants the hot slurry from
the digester is returned through the outer pipe. the digester is flashed in a series of pressure
This tube digester has been modified by placing vessels until it reaches the atmospheric boiling
several tubes for the cold slurry in parallel in- point. The steam generated in flashing is used in
side a larger outer tube. This reduces the length heat exchangers to heat the flow of liquor and
of the unit. The variety of digester design is illus- bauxite coming to the digester. Flashing also re-
trated in Figures 9, 10. The flow through single- moves water from the process stream, thereby
digester units may be as high as 12 m3 /min. accomplishing a significant portion of the evap-
oration needed. Normally, heaters are tubular,
but coils of tubing also are used. As few as three
stages of flashing may be needed when the di-
gestion temperature is 418 K, and this may be
increased to ten stages for a unit operated at
515 K. Figure 9 is a schematic diagram of a high-
temperature digestion unit.

Heat Exchangers. Operating practice has

been divided as to whether the bauxite slurry
should be heated separately or whether it should
be mixed with the rest of the solution and then
Figure 10. Tube digester heated. These two modes of operation have been
a) Piston pump; b) Heat; c) Condensate; d) Flow control designated the single- and the double-stream
valve; e) Steam processes. Those favoring separate heating of
The usual construction material for digesters the bauxite slurry, the double-stream option,
is mild (low-carbon) steel, despite data show- feared rapid deposition of desilication product
ing that, at the temperatures and NaOH con- on the heat-transfer surfaces. Experience has
shown that, particularly if the bauxite slurry is
 Aluminum Oxide 17

stored for blending, those fears are unfounded. ature, solution concentration, and degree of de-
The rate of fouling is no higher than for heat- silication. The holding time is fixed by the design
ing clean liquor. In both options there is slow of the digester vessels. As noncondensable gases
deposition of desilication product on the heat- are formed by the reaction of the solution with
exchanger surface because the desilication reac- organic materials in the digest, it is necessary
tion does not reach equilibrium in the digester to vent these gases so that the digester remains
and continues at a slow rate wherever the solu- full. Venting can be controlled by sensing the
tion temperature is raised. The encrustation must liquid level with a float or a radioactive sensor.
be removed periodically by washing with dilute Temperature measurement and control are rela-
HCl or H2 SO4 , or by mechanical means to main- tively simple because only the temperature from
tain a high heat-transfer rate. the final heater is critical. Concentration control
In some plants using the double-stream sys- comes from blending the bauxite and careful
tem, the bauxite slurry is heated in contact proportioning of the slurry and clean solution
heaters. These heaters are designed much like flows. Originally, feedforward control was used
barometric condensers. The liquid is forced to in which the composition of the incoming ma-
fall through the steam in the heater in droplets terials was used to set the rates at which they
or in thin films. The large surface area exposed were added. In modern practice feedback con-
results in high heat-transfer rates, and because trol is based on the composition of the exiting
there is no metallic surface, there is no fouling. solution. Chemical analyses of the solution can
The penalty is higher dilution. be used, but the time lag involved makes this
The heat needed to raise the temperature control imprecise. Nearly real-time control has
above that achieved in the flashing system can been achieved by using the fact that the con-
be introduced by direct injection of steam. More ductivity of the solution at a given temperature
often the final heating to the digest temperature is a linear function of the mass ratio of Al2 O3
is done in a separate heat exchanger, with the and NaOH. This is the variable of interest. In
energy coming from steam, hot oil, or molten modern plants the output of the sensor goes to a
salts. computer, which in turn controls the amount of
bauxite slurry pumped. Such control has reduced
Pumps. Centrifugal pumps are used in most the variance in concentrations to about a third
digester systems. Those used for pumping slur- of the values experienced earlier. This permits
ries are built of wear-resistant alloys. A great operation closer to the maximum safe concen-
deal of maintenance is required to keep the shaft tration with less risk of premature precipitation
seals operating well. In some plants, concern of Al2 O3 in clarification.
about pump wear has led to the use of diaphragm
pumps. In such pumps a check valve admits the
slurry to a chamber on one side of a flexible di- 3.1.4. Residue Separation
aphragm. When that chamber is full, oil at high
pressure is forced into a chamber on the other The next step in the process is the separation of
side of the diaphragm. This moves the slurry bauxite residue solids from the solution. A wide
through another check valve into the digester. variety of equipment and procedures is used in
Therefore, no rapidly moving parts are in con- this operation. The methods chosen depend on
tact with the slurry. In a Japanese modification, the quantity and properties of the residue.
called the Hydrohoist, the diaphragm is replaced The particle size distribution of the residue
by a sphere that is free to move the length of a solids is usually bimodal. The coarse fraction
cylinder. Slurry is kept in one end of the cylinder over 100 µm in diameter is termed sand, whereas
and the drive fluid, which is clean process solu- the rest of the solids are finer than 10 µm. The
tion, is in the other end. Because of this choice of sand fraction may range from 5 to nearly 50 %
drive fluid, leakage past the sphere is of no con- of the total. The lowest amounts are in the
sequence and tight clearances are not required. Caribbean bauxites and the highest are in the
residue from Western Australian bauxite. In the
Measurement and Control. Operating plant the sand fraction is separated from the pro-
variables that must be controlled are temper- cess stream in liquid – solids cyclones or in more
18 Aluminum Oxide

Figure 11. Residue thickener

a) Feedpipe; b) Feedwell; c) Motorized lifting device; d) Liquid level; e) Overflow launder; f) Weir; g) Off-tank support;
h) Tank; i) Cone scraper; j) Discharge cone

primitive settling devices. A variety of equip- to elevate the units to provide access to a center
ment, including Dorr, Hardinge, and Aikens discharge.
classifiers, have been used to wash the sand free The fine solids behave as a relatively stable
of process solution before it is discarded. In all colloidal suspension, so they settle slowly if not
of these units the sand moves countercurrently treated further. The addition of flocculants im-
to the wash water so that a maximum of wash- proves the clarity of the thickener overflow, the
ing is done with a minimum of water. The wash settling rate of the solids, and the solids content
solution is added to the balance of the process of the underflow pulp. Flocculants act by binding
flow and proceeds to further clarification steps the very fine particles into flocs that may be sev-
for removal of the fine solids. eral millimeters in diameter. The ratio of mass to
In most plants the fine residue fraction is set- drag forces is increased so the flocs settle more
tled in raking thickeners of the type illustrated in rapidly.
Figure 11. These vessels may exceed 49 m in di- Starch from grains or roots was the first
ameter. Some older plants used multideck thick- flocculant; the dosage varied from 0.5 to 3 kg
eners. Difficulties in keeping the multideck units per tonne of bauxite. The amount required in-
in balanced operation have led to almost exclu- creases as the surface of the residue increases
sive use of single-deck units in new construction. and is affected by the mineral composition of
The desanded slurry is fed at the center of the the residue. Starch has the advantages of be-
thickener and clarified solution overflows at the ing inexpensive and ubiquitous. It does react
perimeter. As the solution flows radially across with the NaOH in the solution to add organic
the thickener, both the horizontal and vertical compounds to the solution. In the 1950s water-
velocities become very low. The solids, having dispersible polymers were proposed as floccu-
a higher specific gravity than the solution, sink lants. The first compounds were effective when
to the bottom of the thickener. A settling rate of added at 10 % of the starch charge, but they
1.5 m/h is sufficient for commercial operation. were expensive so they offered no economic
The solution overflowing the thickener usually advantage. More recently, flocculants based on
contains less than 0.3 g/L solids, whereas the un- acrylate – acrylamide copolymers have begun to
derflow ranges from 15 to 35 wt % solids. The replace starch. The functional groups of these
rotating mechanism has plows mounted at an anionic flocculants can be modified to suit spe-
angle to the arm. These slowly move the set- cific operating conditions. Different materials
tled pulp across the bottom of the thickener to a may be used in the thickeners and in the wash-
discharge port. A few units have been designed ing operation. In some cases a small amount of
with the discharge at the perimeter rather than at starch is added to the synthetic flocculant to im-
the center. The objective was to avoid the need prove overflow clarity. These synthetic materials
 Aluminum Oxide 19

now offer an economic advantage because they charging at 55 % solids are more effective than
have been made less expensive and more effec- six stages operating at 20 % solids.
tive. Another approach only recently introduced
With the residue concentrated in the thickener into plant practice is called the deep thickener.
underflow, the next task is to wash it free of pro- This equipment was developed in the British
cess solution so that it can be discarded. This is coal industry to concentrate the slimes from coal
usually done in countercurrent decantation sys- washing. In the deep thickener, increased quan-
tems using washing thickeners that are similar tities of flocculant are used, and a column of
in design to those used for settling. The washing residue pulp up to 10 m deep is maintained. The
operation is done in as many as seven stages with hydraulic pressure of the deep column appears
the solids moving countercurrent to the wash to densify the pulp so that underflow solids ap-
stream. This is illustrated in Figure 12. An equa- proaching the concentration of filter cake are ob-
tion can be written for each stage expressing a tained. The overflow from these units contains
material balance between soluble materials and more solids than the flow from standard thicken-
dilution. Computer models of the washing sys- ers, but the units are finding use in concentrating
tem allow accurate prediction of performance. residue for washing and for disposal. The sim-
plicity of the equipment adds to its appeal.
The final stage of clarification is polish fil-
tration of the solution, sometimes called clear
pressing. Most of the residue solids have been
removed from the process solution in the previ-
ous steps, but product purity must be protected
by removing the few particles of solids remain-
ing. Filter presses are used most widely.
Another approach to polish filtration is use
of a stationary filter in which the medium is uni-
Figure 12. Flows at stage n in countercurrent decantation form, fine sand a meter deep. Gravity provides
(O = overflow; U = underflow) the force to move the solution through the sand
bed. During operation, the fine solids are mixed
In residue washing, the objective is to mini- with the sand, from which they are elutriated at
mize both the value of the soluble salts lost and the end of the cycle. Such filters can be auto-
the cost of evaporating the added wash water. mated and are especially effective with residues
The solubles in the discarded pulp can be re- that are difficult to process.
duced by increasing the solids content of the Close attention is required to keep the solids
underflow. This reduces the amount of solubles content of the filtrate down to 0.5 mg/L to protect
carried from one stage to the next so that dilution product purity. Light transmission of the filtrate
is more effective and can be accomplished by us- is used as an index of clarity. Purity originally
ing more flocculant or by increasing the holding was determined visually, but nephelometers are
time in the thickener. There is some risk in the used now. If evidence of solids is found, the fil-
latter change. If some undissolved gibbsite or trate from each filter is scanned to locate the
boehmite remains in the residue, it may induce source. Some solids may pass through the filter
precipitation with a resulting loss of Al2 O3. cloth before a layer of solids forms to serve as a
In some plants vacuum drum-type washing barrier, so it is common practice to recycle the
filters are used to replace some or all of the wash- first portion of filtrate.
ing thickener stages. The solids content of the Control in clarification has two major objec-
residue may be increased to 50 – 60 wt % by fil- tives; the solids must be removed and the washed
tration. Therefore, only about 33 % as much so- residue must be prepared for discard, using a
lution is needed compared to plants using thick- minimum of wash water. The first objective is
eners and this results in a great increase in the achieved by measuring the cloudiness of the fil-
effectiveness of washing. Calculations for coun- trate. High solids in the underflow are dependent
tercurrent washing show that two stages dis- in part on the retention time in the thickener, so
measurements must be made of the pulp level in
20 Aluminum Oxide

the unit. Automatic determination of the inter- in the diagram above a lower point on the solu-
face between clarified liquid and pulp has been bility curve.
done by ultrasonic and by optical scanning. The
density of the underflow pulp is monitored by a
device that measures absorption of radiation or
by gravimetric measurement. If the pulp is too
dilute the rate of withdrawal is decreased. This
control can be overridden if the pulp level in the
unit rises too high so that there is concern that
the solids in the filter feed may become exces-
sive. The flows of solids and wash water also
must be measured and proportioned for efficient
operation.

3.1.5. Precipitation

The filtered solution has a temperature of 375 K

and it must be cooled to 335 – 345 K before pre-
cipitation. This cooling is usually done in a flash- Figure 13. Generalized solubility curve
ing system analogous to that used in recovering The kinetics of the precipitation reaction are
heat in digestion. Because the temperatures are represented by the equation:
below the atmospheric boiling point, the flash
vessels and the heat exchangers must operate un- −dc
= kexp (−E/RT ) A (c−c∞ )2
der vacuum. Most of the heat removed by flash- dt
ing is transferred to the colder solution return- where:
ing from precipitation. Plate-type liquid – liquid c = Al2 O3 concentration, g/L
heat exchangers have also been used. The solu- k = constant
tion can be cooled further midway through the E = activation energy, about 59000 J/mol
precipitation operation. This allows higher re- R = 8.31441 J mol−1 K−1
covery of Al2 O3 without using conditions that T = temperature, K
lead to excessive nucleation of product. A = seed area, m2 /L
Recovery of the Al(OH)3 from the process c∞ = concentration at equilibrium
solution is known as precipitation, decomposi-
tion, or Ausrührung. The reaction is the reverse The reaction is second order, i.e., the rate is
of the digester reaction given earlier. The cool- affected by the square of the difference between
ing done after digestion and filtration has moved the actual Al2 O3 concentration and the equilib-
the solution into an area of the solubility diagram rium concentration. The operating temperature
known as the metastable region. The concentra- affects the equilibrium concentration and the re-
tion and temperature are such that the solution is action rate. Because seed area is important, the
supersaturated with Al(OH)3 but is not saturated seed charge must be as high as can be maintained
enough for spontaneous crystallization. This is while meeting other operating objectives.
illustrated by Figure 13. At the digest tempera- The first objective in precipitation is to pro-
ture, T 1 , the Al2 O3 concentration is increased to duce Al(OH)3 that, when calcined, meets the
point P on the diagram. Cooling to temperature specifications for metallurgical alumina. These
T 2 results in crossing the solubility curve into the specifications are discussed in Section 5.2. The
metastable region. Addition of Al(OH)3 seed at second objective is to obtain a high yield from
this point causes precipitation and the concen- each volume of solution. This increases the plant
tration of Al2 O3 approaches the solubility curve capacity and reduces the amount of energy spent
at T 2 . The additional cooling recently adopted in heating and pumping the solution. At the
moves the solution conditions further to the left same time, the processes serving to create new
Al(OH)3 particles must be controlled so that the
 Aluminum Oxide 21

number of seed particles created equals the num- ticles are obviously the result of agglomeration.
ber of particles leaving the system as product. Those agglomerates having fewer particles can
This requires balancing nucleation, agglomera- be shown by thin-section micrographs to have
tion, growth, and particle breakage, so a combi- grown radially from an agglomerate of relatively
nation of science and art has developed. few nuclei.
About 2 × 1010 nuclei must be formed in In Figure 15, the Al2 O3 concentrations in ex-
each liter of solution to balance the process. The perimental precipitations is shown as a function
rate of nucleation is a strong function of both of time and temperature. The slopes of these
the degree of supersaturation and of temperature. curves indicate the rates at which precipitation
Very few nuclei are formed if the temperature is is progressing. All curves show a high rate at
above 350 K. A change in the operating temper- the start and appear to be approaching a final
ature of only 5 K will change a system from a net value asymptotically. The final concentrations
producer to a net consumer of nuclei. Tempera- were well above the saturation level, but in these
ture changes of 2 – 3 K are the most frequently as in plant operation the rate became unusually
used control measures. low, so the process was terminated.
The nuclei grow by accumulation of Al(OH)3 Precipitators are vertical cylinders; the
on their surface if they become large enough to height, which may be 30 m, is usually 2.5 – 3.0
be viable seeds. The rate of growth can be as high times the diameter. The seeded slurry is circu-
as 9 µm/h, but it is generally much lower. The lated to maintain intimate contact between solids
growth rate is independent of the particle diame- and solution. Early precipitators circulated the
ter. Particles also increase in size by agglomera- material by means of a central air lift pipe. Air
tion. By a process that is not well understood, the introduced at the bottom of the pipe reduced the
nuclei form clusters in the first few hours of the apparent density of the slurry within the pipe.
cycle in batch precipitation. When the supersat- This caused slurry to flow into the bottom of the
uration is low, this agglomeration does not occur. pipe to establish circulation. Modern precipi-
Some speculate that when the rate of precipita- tators are circulated mechanically by impellers
tion is high, the Al(OH)3 is not well crystallized up to 3 m in diameter operating in a draft tube.
when it is first deposited on the seed. This later In these units the flow is downward through the
may serve as the bond for agglomeration. At low tube, so the tank bottoms are nearly flat to re-
supersaturation the deposited material is better verse the flow and cause upward motion of the
ordered. The action of mechanical equipment in slurry. Tanks with air lifts have conical bottoms
precipitation can break fragments off crystals or to direct the flow to the central air lift.
break up agglomerates, creating secondary nu- Originally, precipitators were filled individu-
clei, but this is not a major factor in most plants. ally in batch operation. This method had several
disadvantages, chief of which was the need for
many operators because the operating cycle of a
single precipitator required at least 15 separate
operations. Control was difficult and batch op-
eration left equipment out of service part of the
time.
Nearly all plants built in the last 30 years have
used the continuous system. Up to 13 tanks are
placed in series so that the flow of seed and solu-
tion moves by gravity through channels connect-
ing the tank tops. Continuous flows are much
easier to measure and to automate. The number
of flows is reduced, so control is better and the
labor requirement is reduced. There are some
Figure 14. Technical aluminum hydroxide (gibbsite) operating problems. One is to avoid passage of
Figure 14 is an electron micrograph of some the slurry across the tank tops, thereby reduc-
Al(OH)3 produced in a plant operation. The par- ing the retention time. Movement of solids from
tank to tank is also a problem. An ideal system
22 Aluminum Oxide

Figure 16. Al2 O3 concentration profiles in batch and con-

tinuous precipitation
Figure 15. Effect of temperature on precipitation

would retain fine particles in the tanks and move before becoming product. This reflects the be-
only the coarse material to the discharge. This is lief that the agglomerates must be made tougher
not possible, so a compromise method of oper- by deposition of additional Al(OH)3 so that they
ation must be found. Precipitation takes place at do not disintegrate in calcination and subsequent
constant conditions in each tank instead of fol- handling.
lowing a continuous curve, as in Figure 16. This In a modification [47], a relatively small
tends to decrease production per tank, but the charge of fine seed is added to the first tank in a
loss is more than recovered because the tanks series. This promotes agglomeration. Then, ad-
are always in use. ditional coarser seed is added to the second or
Several patterns have been used to supply the third tank to provide the large seed area needed
seed for precipitation. The earliest was to neu- for high production. As indicated previously,
tralize a portion of the solution. An Al(OH)3 gel cooling may be done between units in a series
was precipitated that changed into fine crystal- to increase the supersaturation in the final tanks,
lites on aging. This very fine material was grown thereby increasing the production rate. A fur-
through at least one cycle to provide an active ther change in modern plants is to filter the seed
seed for product precipitation. The more com- slurry being recycled. This decreases the amount
mon approach is to use fine particles, produced of spent solution returning to the system and in-
in the operation, as seed. The slurry leaving pre- creases both the Al2 O3 concentration in the first
cipitation is classified into a coarse product frac- tank of the series and the overall production.
tion and one or more fine fractions. The fines The control variables available to the pre-
are returned to the process to grow to product cipitation operator are the temperatures in the
size. Classification is done by controlling the system; the flow per unit, which translates into
flow rate through tanks so that the fines are elu- holding time; the amount of seed; and the parti-
triated. Liquid – solid cyclones are coming into cle size of the seed. Some of these variables are
use because they provide more accurate sepa- difficult to control, so the system usually cycles
rations. The seeding and classification systems slowly from coarser than desired to finer. There
have become increasingly complex. In modern is enough inventory in the process so that minor
plants at least three fractions are separated. In cycles can be tolerated without affecting plant
some plants the agglomerates formed from fine output.
seed must pass through the system once more
 Aluminum Oxide 23

3.1.6. Impurities content. Only in the production of high-purity

metal has there been concern about the gallium
The impurities in the product Al2 O3 are affected content of alumina. About 10 t/a of gallium is
by all of the foregoing operations, including se- recovered from Bayer process solutions. This
lection of the bauxite. There are at least three is the best source for the production of gallium
classes of impurities. The first is residue solids ( → Gallium and Gallium Compounds).
that are not removed in clarification. The large Silicon is a component of many aluminum al-
surface area of Al(OH)3 in precipitation effec- loys, yet the specification for Al2 O3 is less than
tively sweeps up these solids into the product. 0.02 % SiO2 . This value is only 25 % of that
The preventive measure is increased vigilance specified 50 years ago. The SiO2 is in solution,
in filter maintenance and operating. The second but it appears to be added to the product through
class is materials that are in true solution, such a slow continuation of the desilication reaction
as sodium and gallium. The third group includes (Section 3.1.2). There is also evidence that if the
materials that are in solute form at the tempera- rate of Al2 O3 deposition on seed is not high,
ture of digestion but precipitate later in the pro- the seed surface becomes at least partially cov-
cess. Their solubilities may be only milligrams ered with desilication product, thereby becom-
per liter and return of the solution to equilibrium ing less active as a seed for Al(OH)3 precipita-
at lower temperature may be slow. If precipita- tion and more active toward SiO2 . This impurity
tion is not completed before filtration, the re- is controlled by driving the desilication reaction
maining impurities appear in the product. There nearer to completion. Lowering the SiO2 con-
are also other impurities that do not fall neatly centration of the solution below 0.1 g/L gives a
into these categories. product containing less than 0.003 % SiO2 .
Sodium is the main component of the process Potassium is undesirable in the Al2 O3
solution and is also the largest contaminant of the because it may destroy the graphite in
product. The Na2 O content of alumina can be de- Hall – Héroult cells by intercalation, i.e., it dif-
creased by increasing the seed charge and by in- fuses between the layers of the graphite struc-
creasing the precipitation temperatures. The real ture, thus expanding its volume. Although it is
variable that these operating changes help con- soluble in Bayer solutions, there has not been
trol is the rate of crystal growth. Higher temper- a recorded instance of K2 O concentrations be-
atures, greater seed area, and lower Al2 O3 con- coming high enough to affect the Al2 O3 quality.
centrations all slow growth and give impurities Iron(III)oxide (Fe2 O3 ) as an impurity in
more time to diffuse from the surface. By proper Al2 O3 has been the subject of much investiga-
control of these variables an order of magnitude tion. It is soluble up to ≈ 0.1 g/L in the solu-
decrease in the Na2 O content of a commercial tions at digest temperatures (400 – 500 K), but
product has been achieved. Some sodium is lost only to ≈ 0.001 g/L at 333 K [48]. This recon-
in the Hall – Héroult cells during smelting by ab- ciles the observations that Fe2 O3 behaved at
sorption into the cell lining and by conversion to times as if it were in solution and as a colloid at
sodium metal, so complete absence of sodium others. There are several iron minerals that can
in metallurgical alumina is not necessary. The serve as sources for the impurity. Hematite (α-
target is to balance the input to the cells with Fe2 O3 ) and goethite (α-FeO(OH)) are present
the losses. This requires Al2 O2 containing about in most bauxites. Goethite is slowly converted
0.4 – 0.5 wt % Na2 O. to hematite in high-temperature digests, particu-
Gallium is a ubiquitous component of alu- larly if CaO is present. This conversion improves
minous ores. Its chemistry is similar to that of clarification because hematite settles better than
aluminum, so it accumulates in Bayer process goethite. The mineral siderite (FeCO3 ) present
solutions until an equilibrium is reached at about in some bauxites not only is a source of iron but
0.2 g/L. The gallium content of Al2 O3 is a lin- also reacts with NaOH to increase the amount
ear function of the gallium concentration in the of causticization needed. Pyrite (FeS2 ) is almost
solution. Therefore, the amount leaving in the insoluble in Bayer solutions; its adverse effects
product equals the input. Because gallium is in occur when the sulfur is oxidized to sulfate in
true solution, the same changes that lower the the presence of air and water. The sulfate will
Na2 O content of the product lower the gallium
24 Aluminum Oxide

react with NaOH to form Na2 SO4 which has to sulfate salt is removed by evaporation and crys-
be removed periodically. tallization. The least soluble salt is schairerite
Paradoxically, there is less difficulty with (Na2 SO4 · NaF), and when the fluoride ion is de-
Fe2 O3 as an impurity in processing bauxites pleted, burkeite (2Na2 SO4 · Na2 CO3 ) appears.
containing a large amount of iron oxides. This is The fluoride ion is almost never present in quan-
probably because the iron oxides serve as seed tities large enough to be harmful.
and hasten hydrolysis of the NaFeO2 formed in Many bauxites contain phosphate miner-
the digest. Running the solution over iron oxide als. Apatite (3Ca2 P2 O8 · CaF2 ) does not re-
particles before filtration has been effective in act in the process; indeed, this compound or
controlling this impurity. Another process for its hydroxy counterpart is formed when solu-
lowering the iron content of Al2 O3 is termed ble phosphates react with calcium in the di-
step precipitation. The filtered Bayer solution is gest. Aluminum phosphates, such as wavellite
lightly seeded with Al(OH)3 for a short time to (4AlPO4 · Al(OH)3 · 9H2 O) do react, forming
precipitate up to 3 g/L Al2 O3 . The seed and the Na3 PO4 as the soluble phosphate. The phos-
small amount of precipitation effectively sweep phate ion interferes with flocculation of bauxite
the colloidal iron hydroxide particles from the residues containing goethite, probably by com-
solution, leaving an Fe2 O3 concentration of less peting for attachment sites [49]. The concentra-
than 0.005 g/L. tion of phosphates never is high enough to inter-
Calcium also is a common impurity. The fere with Al2 O3 purity. Addition of CaO to the
presence of increasing amounts of Na2 CO3 in digest is the control measure.
the Bayer solution seems to increase the CaO Organic matter in bauxite, whether it be
in the product. The calcium content of alumina, roots and twigs from plants or humic acids from
as with sodium, needs to be controlled such that decayed matter, reacts in the digest to form a
the Hall – Héroult cell bath can come to an equi- wide variety of organic compounds. Some op-
librium level acceptable for cell performance. eration process streams have exceeded 15 g/L
Calcium can be controlled by step precipitation organic carbon in solution. There is evidence
or by lowering the carbonate content of the so- that larger molecules are oxidized in the pro-
lution. cess all the way to Na2 CO3 and sodium oxalate
Lithium is also acceptable in Hall – Héroult (Na2 C2 O4 ). In addition some, but not all, of the
cells. It can be removed by step precipitation. organic compounds may interfere with precipi-
Other metallic impurities that appear in tation [4].
many bauxites in small amounts are chromium, The effect of sodium oxalate on process-
copper, manganese, titanium, vanadium, and ing has not been quantitatively determined, yet
zinc. Generally, these impurities are not so con- many plants incorporate equipment for crystal-
centrated that removal processes are required. lization of the oxalate salt from the solution. Oth-
Sulfide salts have been added to precipitate cop- ers wash this salt from the Al(OH)3 seed and
per and zinc. The chromium is a problem only if recover it from the wash water. The evidence is
it is oxidized; the organic salts in the solution are overwhelming that operations are improved by
usually a sufficient reductant. The addition of the oxalate removal techniques. Early removal
manganese compounds as oxidants for organic processes included evaporation to high concen-
material has been reported. trations followed by centrifugal separation of the
Anions, such as carbonate, chloride, fluoride, gelatinous salt mass. In other plants, a portion of
and sulfate, are known to interfere with Al(OH)3 the solution was mixed with bauxite or Al(OH)3
precipitation. The carbonate ion is controlled and heated to 1280 K. This destroyed the organic
by addition of lime, although processes have compounds and formed NaAlO2 , which could
been reported in which Na2 CO3 is removed by be recovered in the process. A German process
evaporative crystallization or by cooling the so- adds magnesium salts to the digest to remove the
lution to 260 K. The sulfate and chloride ions deleterious organic compounds. Still others are
usually are controlled naturally, as their salts investigating methods of oxidizing the organic
are incorporated in the desilication product in material in the solution [50].
sufficient quantities to maintain an equilibrium.
There are commercial operations in which the
 Aluminum Oxide 25

3.1.7. Calcination coolers fluidize the product Al2 O3 around heat-

exchange surfaces, often in several stages. In
The final operation in production of alumina is such coolers, the heat can be recovered in com-
calcination. The temperature of the Al(OH)3 is bustion air or in wash water and the product can
raised above 1380 K resulting in the reaction: be cooled readily to 425 K.
The progressive adoption of large-capacity
2 Al(OH)3 → Al2 O3 + 3 H2 O stationary calciners has reduced fuel consump-
tion for alumina calcination to ca. 3.1 GJ per
As discussed in Section 2.2, this reaction can tonne of alumina, which compares to ca. 4.5 GJ
take several pathways and several transition per tonne for earlier rotary kilns. Several sta-
forms may appear. The end of all pathways is tionary calciner designs with capacities of
α-alumina. In older European practice, a ma- > 2500 t/d alumina are now commercially avail-
jor portion of the alumina was converted to the able. In stationary calciners, a combination of
α-phase, sometimes by the addition of a fluo- fluid beds and stages in which the solids are
ride salt to lower the temperature of transforma- transported in suspension is used. Figure 17 is
tion. In American practice, calcination always a schematic diagram of a commercial unit capa-
has been less severe; so, normally,
20 % of ble of calcining 1500 t/d.
the alumina is in the α-phase. The Al(OH)3 is washed and dewatered on the
Before calcination, it is necessary to wash the filter (a) and is conveyed into the flash dryer (b),
process solution from the coarse Al(OH)3 . This where it encounters hot gas from cyclone (g).
is done countercurrently, using storage tanks and The gas evaporates the free water from the par-
filters. As in residue washing, increasing the ticle surfaces. Because the temperature exceeds
number of washing stages and the concentration 480 K, a portion of the water of hydration also is
of solids leaving each stage improves the effec- driven from the crystals. Cyclone (c) separates
tiveness of washing. Vacuum filters of several the solids from the gas. The gas, cooled almost
designs have been used for the final separation. to its dew point, leaves the unit through the elec-
The early Oliver and Dorr drum filters have been trostatic precipitator (j), where dust is recovered.
replaced by horizontal rotary filters because bet- Vessel (d) serves as a surge buffer to smooth the
ter washing can be achieved. The quality of the flow of solids through the unit. The solids are
wash water is of some concern because such im- separated in cyclone (g) to enter the vessel (f)
purities as calcium and magnesium can be ad- where combustion of fuel is taking place. Vessel
sorbed on the surface of the Al(OH)3 . (e) allows a holding time at the calcination tem-
Earlier, calcination was done in reverberatory perature so that the water content of the product
furnaces. These had neither the capacity nor the is low. A small amount of fuel can be burned in
thermal efficiency required, so they were soon this vessel if a higher temperature is desired. In
replaced by rotary kilns. These kilns are cylin- this design the flow of solids is counter to the
ders that may be 3.5 m in diameter and over 80 m flow of the gas.
long. They are mounted on bearings and rotate The solids are cooled, also in counterflow, by
about an axis inclined at a small angle to the the combustion air in unit (h). Final cooling is
horizontal. Damp Al(OH)3 from the filters en- in a fluidized bed unit (i). In the fluidized unit
ters the upper end and slowly tumbles toward a small amount of air is introduced through a
the lower end, traveling against a stream of hot membrane at the bottom. This lifts but does not
gas formed by combustion of natural gas or oil entrain the solids, so they behave much like a
at the discharge end. Early kilns were less than fluid. Heat is transferred at a high rate to air or
40 m long, but longer units have better thermal water flowing through tubes submerged in the
efficiency and higher capacity. bed. The product Al2 O3 can be cooled below
Product coolers were added to kilns so that 400 K with all of the recovered energy being
part of the heat in the incandescent product could used in the process.
be transferred to the combustion air. Early cool- The great advantage of the stationary units
ers followed designs developed in the cement is that the heat required for calcination is
industry and were themselves rotary units much 3100 MJ/t. The capital costs are lower than for
like, although smaller than, the kilns. Improved rotary kilns of equal capacity, and the mainte-
26 Aluminum Oxide

Figure 17. Alcoa flash calciner

a) Filter; b) Flash dryer; c) Cyclone; d) Fluidized-bed dryer; e) Holding vessel; f) Furnace; g) Cyclone; h) Multistage cyclone
cooler; i) Fluidized-bed cooler; j) Electrostatic precipitator

nance costs are lower primarily because the re- mina quality in modern stationary calciners are
fractories are not subjected to rotational stresses. reviewed in [51].
Because the capacity per unit is high and au-
tomation is quite easy, the labor requirements
are low. The stationary units are being installed 3.1.8. Evaporation
in retrofitting older plants as well as in new con-
struction. As is shown on the flow sheet for the Bayer pro-
Alumina calcined in stationary kilns has cess (Fig. 7), the solution continuously cycles
a lower α-alumina content and a higher sur- through the plant. Consequently, any wash wa-
face area than alumina calcined at the same ter used must be evaporated so that the solution
temperature in a rotary kiln. This reflects the volume can be controlled. About 10 % of the
shorter residence time and the absence of a high- flow is evaporated in the two cooling areas by
temperature flame in the static units. Photomi- being flashed into steam. In high-temperature
crographs show that the rapid temperature rise digesters, the amount of flash evaporation is
creates vapor pressure within the particles that even larger. At least one plant processing high-
tends to fracture large crystals. grade bauxite was designed without any addi-
The characteristics of the metallurgical alu- tional evaporation capacity. In most cases, the
mina are controlled mostly by the time and tem- economics require installation and operation of
perature of calcination. The important parame- evaporators. The objective is to minimize the
ter is the reaction between the Al(OH)3 feed and summed costs of evaporation and the value of
the flow of fuel. The fuel must be free of impuri- the soluble salts lost by incomplete washing. The
ties that can contaminate the alumina. Sulfur and minimum is usually attained with a net dilution
vanadium in fuel oil are limited by concern for of the residue of 1.5 – 2.0 kg/kg.
product purity. The amount of combustion air Table 7 lists the input and exit streams that
must be sufficient to burn the fuel completely compromise the dilution balance in an operat-
without the use of a great excess that increases ing plant. Efficiency demands that all of these
the gas flow and thereby reduces the thermal ef- flows be monitored.
ficiency. Factors affecting fuel economy and alu-
 Aluminum Oxide 27

Table 7. Dilution balance

Evaporators are controlled primarily by
changing the amount of steam used. The flow
Inputs Losses of feed solution is regulated so that crystalliza-
residue wash evaporation tion of soluble salts is either induced or avoided,
sand wash – depending on the operating mode. Temperature
Al(OH)3 wash heat interchange flash readings at each effect are compared to design
free moisture in bauxite Al(OH)3 to calcination
water in gibbsite and boehmite free water with Al(OH)3 values to indicate operating difficulties.
injected steam water with residue
purge water vapor from solution surfaces
sodium hydroxide
cleanup water (maintenance) 3.1.9. Residue Disposal
uncontrolled dilutions
The most important environmental problem in
Several evaporator designs are used in Bayer the Bayer process is disposal of the bauxite
plants, but nearly all designs are used in multiple- residue. The solution left with the residue af-
effect configurations. In such units each stage ter an economical amount of washing is still
operates at a lower pressure than the preced- very alkaline and cannot be allowed to contam-
ing one. Therefore, the vapor evaporated from inate ground water. Furthermore, the desilica-
the solution in the first stage is at a temperature tion product in the residue which is in contact
high enough to heat the solution in the second with water has the capacity to exchange sodium
stage, causing it to boil. This continues to the for hydrogen. An aqueous slurry of the residue
final stage, where the vapor is condensed. The that had been washed with 1000 times its mass
condenser operates under vacuum so a jet pump of distilled water still reached a pH value of
is necessary to remove noncondensable gases 10.5 on standing. The undrained fine residue,
from it. The more times the latent heat is used, even after years of consolidation, does not have
i.e., the more stages that are present, the more enough strength to support buildings or equip-
water can be evaporated by the fuel steam used ment. These properties make disposal a difficult
in the first effect. With Bayer solutions the maxi- problem.
mum number of effects is six. This is because the Previously, disposal was to a marine environ-
boiling point of the solution is elevated 5 – 8 K ment where the alkalinity was diluted by large
by the dissolved solids. This reduces the steam quantities of water. This method has been used
temperature in each effect; with many effects in the seas off Europe and Japan and in a river in
there is little temperature difference available to the United States. Studies by environmentalists
cause evaporation. have indicated little damage to flora or fauna by
An unconventional design called continuous the residue in a disposal area [52]. Today, how-
regenerative evaporators has been used in some ever, environmental concern is so great that any
plants. These units are similar to the heating and new refinery is unlikely to be permitted to use
flashing equipment used in digestion in that the marine disposal.
feed is heated through up to ten stages with- Early inland refineries simply dammed a con-
out evaporation; the hot solution is then flashed venient valley or built retaining dikes on flat land
through an equal number of stages and the steam to form residue disposal areas. In some cases,
is used for heating the feed. These units are not the sandy portion of the residue was used to
as efficient as most multiple-effect evaporators. build the dikes. This method can be effective and
The design choice is based on economics. Spe- cheap if care is taken to protect the surroundings
cial evaporator designs may be used when it by proper sealing techniques. The compacted
is necessary to crystallize organic or inorganic residue has a lower permeability than many
salts from the solution. In such designs pumps clays; yet, there have been isolated leaks into
are used to increase the thermally induced flow aquifers from such impoundments. Improved
through the tubes in the heaters. The heat-trans- designs have been developed.
fer surfaces in evaporators must be cleaned peri- In Germany, retaining dikes are built with a
odically to remove encrustations of desilication portion of the structure designed to be porous.
product and soluble salts. The dilute solution draining from the residue is
channeled by the porous sections into water-
28 Aluminum Oxide

treatment facilities before being discarded. In Similarly, chemical processes have been devel-
some cases, the dike material exchanged ions oped for recovery of Al2 O3 , Na2 O, and TiO2
with the solution so that little treatment was from residue. Although all are technically possi-
needed. The draining allowed consolidation of ble, none has been feasible economically. Small
the residue so that it could support equipment. quantities of residue have been used in mak-
An American firm used a drained lake in which ing Portland cement, and smaller quantities have
the bottom of the disposal area was covered with been used as a mold wash, as an insulating ma-
sand in which draining pipes were laid. The terial, and, after reaction with H2 SO4 , as a water
residue was pumped to these areas in the tra- treatment. No chemical use is likely to consume
ditional manner as a dilute slurry. Most of the a significant part of the residue [1], [5].
conveying water was decanted, while some per- The residue is claylike and can be used in ce-
colated through the deposit to the drains. This ramic materials. The sodium causes formation of
design has two advantages: the residue consoli- glasses at 1450 K, giving a vitreous bond. Bricks
dates better, so the storage capacity of an area is have been made commercially, but economic
increased, and the hydraulic head on the bottom factors and other shortcomings of the brick have
is reduced to zero, so that leakage is unlikely. eliminated this use. Sintering the residue into ag-
Lakes have been built using the sand drains on gregate for concrete may be economical where
top of seals of clay and plastic film for additional natural aggregate is not available.
environmental safety. In Texas, agronomists have shown that the
Another modern disposal method, called dry residue can be used to neutralize acidic soil,
stacking, takes advantage of the thixotropic na- replacing limestone. The cost of preparing the
ture of the residue. By some method, usually material for application and the logistics argue
vacuum filtration, the residue is concentrated to against extensive use. The conclusion is that
35 – 50 wt % solids. The slurry is agitated to large-scale use of bauxite residue is unlikely, so
reduce its viscosity by as much as two orders efforts should be directed toward reclamation of
of magnitude and pumped to a disposal area. disposal areas.
There it flows in lava-like fashion over the sur-
face, establishing a slope away from the dis-
charge point. In the absence of shear, the vis- 3.1.10. Energy in the Process
cosity of the slurry increases and flow stops.
Water does not separate from the slurry and the Approximately 16 MJ are required to produce
slope causes rain to run off rapidly, so the sur- a kilogram of Al2 O3 . The worldwide range is
face usually is losing water to the atmosphere. 7.4 – 32.6 MJ/kg [48]. Variations in the quality
The surface becomes deeply fissured, further as- of bauxite, plant design, and the size of the plants
sisting drying. In about 90 days the residue may are the reasons for the large differences. Even
dry to 75 wt % solids, far drier than in any of with existing plants, large improvements in en-
the other disposal methods. In this state, it can ergy usage can be made. The Aluminum Asso-
support heavy earth-moving equipment and can ciation (USA) reports that the energy used per
be recovered or used for increasing the height unit of alumina production in 1980 was 68 % of
of retaining dikes. This method maximizes the the energy used in 1972 [54]. The energy used in
storage capacity of a given area and seems to mining is less than 5 % of the total and is difficult
pose the minimum threat to the environment. It to change. The energy for transporting bauxite
does require construction of a permanent lake is double that for mining it, because the aver-
area for water storage and for cooling water. If age tonne of bauxite used in the United States is
any use is to be made of the residue, recovery is transported 4700 km. The situation worldwide is
relatively easy. different because much of the bauxite is refined
Many investigations have been directed to- close to the mines.
ward finding a commercial use for bauxite Within the refinery, more than half of the en-
residue. The high iron content of some residues ergy is used for pumping and heating the so-
suggested production of pig iron. The quality lution and for evaporation. The previous dis-
of the iron was poor and the amount of slag cussion (Section 3.1.3) has shown that plant de-
formed exceeded the original amount of residue. sign can affect heat recovery and minimize en-
 Aluminum Oxide 29

ergy use. Emphasis is being placed on increasing In page 28, values were given showing the
the amount of Al2 O3 recovered from less than fourfold range in energy used to produce alu-
50 g/L to over 65 g/L; some claim yields as high mina. The most important variables are the plant
as 100 g/L. Because energy is more closely re- design and the quality of the bauxite being pro-
lated to the flow of solution than to yield, the cessed. The most energy-efficient bauxites are
energy savings are large. The static calciners are gibbsitic, with very low residue content.
nearly as efficient as they can be made because The capital costs also show wide variation.
the temperatures of the gas and of the product In 1990 U.S. dollars new installations may cost
leaving the units are very low. The change from from $ 700 to $ 900 per annual tonne of capac-
rotary kilns has made up a large portion of the ity. The variables are design factors, location,
savings. There are still opportunities to improve capacity, and the properties of the bauxite to
operating practice and design to reduce energy be processed. Much of the world capacity was
consumption [55]. constructed before construction costs were in-
flated and so has lower capital costs. The effect
of capacity is also large, and plants producing
3.2. Economic Aspects 2 × 106 t/a have costs well below those of plants
producing less than 105 t/a.
The largest cost elements in alumina production Alumina is traded on the world market as a
are raw materials, energy, and capital-related commodity. Not all smelters have alumina ca-
costs for the production equipment. Labor, oper- pacity dedicated to them; they buy alumina on
ating supplies, and miscellaneous costs are much contract. Long-term contracts are common. In
smaller than these three. other instances, alumina is bought when needed
Bauxite is the most important raw material. at spot market prices. Since 1980, alumina has
Its cost includes those for mining, transport, sold on the spot market for less than $ 150 to
levies, and taxes. In addition, the relative qual- over $280 per tonne, reflecting a change in the
ity of the bauxite ore influences the expenditures relationship between supply and demand. Eco-
for necessary reagents. Mining is relatively inex- nomics do not always control production be-
pensive because most deposits are covered with cause many corporations own refineries to sup-
only a shallow overburden and can be mined ply their smelters. In other instances, national
with efficient equipment. Since the formation governments own a significant portion of a re-
of the International Bauxite Association (IBA), finery and for political reasons may choose to
levies and taxes have become a large part of the operate in a noncompetitive situation. Costs per
cost of bauxite. These costs have become rela- tonne of alumina can, under unfavorable con-
tively stable because most are related to the sell- ditions, exceed $ 200, although efficient plants
ing price of aluminum. The availability of baux- may produce at roughly half this figure.
ite from outside the IBA countries has allowed
the effect of supply and demand to influence this
cost. Where levies are not imposed, some sys- 4. Other Processes for Alumina
tem of taxation provides income to the produc-
Production
ing nation. Transportation costs vary from very
small to as much as half the delivered cost of
the bauxite. Some bauxite travels less than 5 km 4.1. Raw Materials
by truck or conveyor belt to the refinery. Other
bauxite may travel more than halfway around Many investigations have sought processes to re-
the world. The characteristics of bauxite most place the Bayer process by using raw materials
important in influencing its value are the avail- other than bauxite [2]. Clay, primarily kaolinite,
able alumina and the reactive silica contents. The has been most considered because it can contain
latter quantity has a great effect on the amount up to 39 % Al2 O3 (→ Clays). Other materials,
of sodium hydroxide and lime required in pro- including anorthosite, nepheline, coal wastes,
cessing. Bonuses are given for high available and fly ash, have been candidate raw materials.
alumina values, and penalties are charged for Yet, less than 2 % of the world supply of alumina
excessive silica. is not made by the Bayer process. This happens
30 Aluminum Oxide

only where use of a domestic raw material and

3 CaO · Al2 O3 + 3 Na2 CO3 + 2 H2 O →
production of a desirable byproduct change the
economic picture. Alumina from ores other than 2 NaAlO2 + 4 NaOH + 3 CaCO3
bauxite normally costs 1.5 – 2.5 times that from
the Bayer process.
Because aluminum is amphoteric, both acid
and alkaline processes have been developed.
Most of the processes in each class follow the
same general flow sheets.

4.2. Alkaline Processes

Sodium compounds, such as Na2 CO3 , react

at 1280 K with the Al2 O3 in aluminous ores
to produce water-soluble NaAlO2 . This com-
pound can be leached from the sinter with water
and the solution treated to remove impurities;
the purified solution is neutralized with CO2 to
recover Al(OH)3 . The last step regenerates the
Na2 CO3 for recycle. Difficulty arises because
the aluminous ores contain SiO2 , which also re-
acts in the sinter to form soluble Na2 SiO3 . In
processing, the desilication reaction discussed in
Section 3.1.2 takes place, so the net recovery of
Al2 O3 is small or zero. If 2 mol of CaO, usually Figure 18. Lime/soda sinter process flow sheet
as limestone, is charged for every mole of SiO2
in the raw material, insoluble calcium silicate In carbonation, Al(OH)3 is formed and the
compounds are formed. Under proper leaching Na2 CO3 solution is regenerated. Nepheline,
conditions the NaAlO2 can be recovered from (Na,K)AlSiO4 , is treated by this process in
such sinters with only slight loss. the former Soviet Union. The calcium silicate
The process has been used commercially in residue is processed to make about 10 t of ce-
two American plants to recover most of the ment per tonne of alumina. The two products
Na2 O and Al2 O3 lost in the desilication product make the process viable here.
formed while treating high-silica native baux- In the Pedersen process, sintering was re-
ite. A schematic flow sheet is given in Fig- placed with a reducing fusion so that ferric ions
ure 18. The same process was investigated by the in the ore were reduced to metal. Iron and the cal-
U.S. Bureau of Mines in a large pilot plant using cium slag were separated by decantation. During
anorthosite as the raw feed [51]. [Anorthosite is a cooling, the CaSiO3 passes through a crystalline
mixture of the minerals anorthite (CaAl2 SiO8 ) phase change and the resulting stresses reduce
and albite (NaAlSi3 O8 ).] Unless the composi- the slag to powder [1], [2].
tion, sintering, and leaching were closely con- The sinter processes suffer economically for
trolled, the residue formed a gel in leaching and several reasons. The energy for sintering and for
became very difficult to filter. evaporation of the leach solution must be added
In a variation of the sintering approach, cal- to the energy required from operations analo-
cium replaces the sodium so that calcium alu- gous to those in Bayer processing. The capital
minate (3CaO · Al2 O3 ) is formed as well as cal- investment is increased by the need for sintering
cium silicate (CaSiO3 ). The calcium aluminate equipment, and although limestone is inexpen-
reacts with Na2 CO3 in an aqueous leach to form sive, the quantity required is so large that the
NaAlO2 . expense is considerable.
 Aluminum Oxide 31

4.3. Acid Processes A hydrated aluminum salt is recovered from

the aqueous solution, usually by evaporation and
All of the acid processes follow the general cooling to cause crystallization. In the hydrogen
flow sheet given in Figure 19. Usually the clay chloride process, advantage is taken of the low
is prepared by grinding and roasting to about solubility of AlCl3 in HCl. The HCl gas is ab-
1000 K. The roasting changes the kaolinite to sorbed in the solution both to regenerate the acid
meta-kaolin, from which the aluminum can be for leaching and to precipitate AlCl3 · 6H2 O. In
dissolved as the acid salt. The roasted clay is all acid processes the hydrated salt is decom-
leached in an acid solution, usually at the atmo- posed to Al2 O3 by heating to 1300 K. Both wa-
spheric boiling point. Some investigators have ter and the acid radical are driven off, and the
chosen to leach at elevated temperature for pro- acid is absorbed for recycling.
cessing advantages even though corrosion prob- The U.S. Bureau of Mines sponsored a coop-
lems become more severe [1]. The siliceous erative effort with several aluminum companies
residue is separated using sedimentation and fil- to investigate acid processes for recovery of alu-
tration as in the Bayer process. Small amounts of mina from clay [56]. For several reasons the HCl
iron salts remain in the clarified solution. These process was preferred: the reagent is inexpen-
salts are removed by extraction with an organic sive, processing conditions are not severe, and
compound that forms a complex with the iron the salt can be recovered without evaporation.
but not with the aluminum salts. The organic so- The HCl is not decomposed in calcination, and
lution is decanted from the aqueous phase and is the water content of the acid salt is half that of
treated to separate the iron salt and to regenerate other acid salts. Despite these features the pro-
the organic extractant. cess is not competitive economically with the
Bayer process. A major fault is the amount of
energy used to roast the clay, to evaporate the
solution, and to decompose the acid salt. The
investment is increased because of the corro-
sive solutions. A process disadvantage is that the
Al2 O3 is physically different from Bayer alu-
mina, so smelting practice has to be changed for
this aluminum source.
Pechiney and Alcan jointly operated a pilot
plant using the H+ process, a modification of
the HCl process in which H2 SO4 is added to
the digest [52]. The combination of acids elimi-
nated the need to roast the clay. Other processes
use H2 SO4 , H2 SO3 , HNO3 , or NH4 HSO4 as
reagents to attack the clay, but no commercial
use has been made of any of them.
Clay is a major impurity of coal, so the ash
from coal may be considered an overroasted
clay. The acid processes, with minor modifi-
cations, will extract alumina from ash [57].
Anorthosite that is high in anorthite reacts with
boiling HCl; this approach has been investigated
in Norway and Canada [58]. So far, all of these
methods have served only to enrich the technical
literature.
Two aluminous minerals that do not contain
silica have attracted attention and, because of
Figure 19. Generalized acid process flow sheet their composition, require different technology.
Alunite, K2 SO4 · Al2 (SO4 )3 · 2Al2 O3 · 6H2 O
[12588-67-9], has been used commercially in
32 Aluminum Oxide

Russia. Both H2 SO4 and K2 SO4 are useful by- Cell Design. New, high current efficiency,
products of alumina production by this method. prebaked anode cells with automatic center-feed
The alunite is heated to drive off the hydrated systems require that the alumina be consistent,
water; additional heating under reducing condi- with trouble-free handling properties to insure
tions decomposes the aluminum sulfate without proper conveying and volumetric metering from
adversely affecting alumina recovery. The solid the feeder. These criteria are best met by a free-
residue from the roast is a mixture of K2 SO4 , flowing, moderate- to low-calcined alumina with
Al2 O3 , and gangue. The K2 SO4 is dissolved relatively coarse and narrow particle size distri-
in water and recovered. Alumina is extracted bution.
from the gangue in a modification of the Bayer
process. In other approaches using alunite, the Cell Gas Dry Scrubbing. The use of dry
solutions are kept acidic so the alumina is re- scrubber systems employing cell-feed alumina
covered as a salt [59]. as adsorbent for fluorides in effluent gas from
Dawsonite, Na2 O · Al2 O3 · 2 CO2 · 2 H2 O the cells dictates other requirements for metal-
[12011-76-6], is found in some oil shales. The lurgical alumina:
temperatures used to recover the oil from the
shale decompose the dawsonite to NaAlO2 , 1) High adsorption capacity for hydrogen flu-
which is soluble in dilute NaOH. The Al(OH)3 oride. This property is closely related to the
and Na2 CO3 can be recovered from the solu- specific surface area of the alumina, which
tion by carbonation. The economics are such is higher for the lower calcined aluminas.
that recovery of the oil must be competitive 2) Attrition resistance.
before mining and byproduct recovery can be 3) Free flowability.
considered. 4) Higher chemical purity to compensate for
capture in the dry scrubber of impurities
which are recycled to the cell.
5. Metallurgical Alumina
Pot Room Working Conditions. Use of
low-calcined, high surface area alumina as a
Aluminum production is the principal applica-
cover for the cell bath reduces fluoride evolu-
tion for alumina; more than 92 % of world alu-
tion within the pot room. Working conditions in
mina production is used for this purpose. The
the smelter are degraded by dust caused by fine
property requirements for commercial metal-
particles of alumina. Reduction of the fines frac-
lurgical alumina are therefore of considerable
tion (< 44 µm) in the alumina and high attrition
importance to the alumina industry. Specifica-
resistance are important for reducing dust.
tions have responded to changes in energy costs,
aluminum cell design, cell gas scrubbing tech-
niques, environmental regulations, working con- Use of Stationary Calciners and Pneu-
ditions in smelters, and the technology for alu- matic Handling Systems for Alumina. The re-
mina calcination. In general, there has been a placement of rotary alumina kilns by the energy-
shift away from relatively small-particle-size, efficient stationary calciners has resulted in pro-
highly calcined, “floury” alumina to a coarse, ducing a different type of calcined alumina for
free flowing, dust-free, less calcined, “sandy” smelter feed. This difference is reflected in the
alumina of narrower particle sizing and higher interrelationship between degree of calcination
chemical purity ( → Aluminum). (measured by the mass loss on ignition), specific
surface area, and the α-Al2 O3 content [60].
The strength of the alumina particles has be-
come of concern not only because of relatively
5.1. Alumina Properties Required for higher breakdown in the stationary calciners,
Smelting but also because of attrition occurring in pneu-
matic unloading and conveying equipment and
Five developments have had a significant impact in fluid-bed dry-scrubbing systems. The gener-
on alumina properties. ation of fine particles in such equipment, apart
from causing unacceptable dusting conditions in
 Aluminum Oxide 33

the smelters, often results in troublesome seg- 6. Industrial Alumina Chemicals

regation problems in alumina storage bins and
bunkers. Alumina, in various forms, is one of the inor-
ganic chemicals produced in greatest volume
Electrolyte Composition and Tempera- today. Although production of aluminum metal
ture. The trend to operate cells at lower temper- consumes ca. 90 % of all alumina, an increasing
atures with electrolyte having a lower bath ratio amount is being applied in the chemical industry
(NaF : AlF3 ) has decreased the solubility and for fillers, adsorbents, catalysts, ceramics, abra-
rate of dissolution of alumina in the electrolyte. sives, and refractories. With the development
The rate of dissolution is greater for aluminas and growth of applications and markets for alu-
having higher surface areas and low content of mina chemicals, all the major alumina producers
α-Al2 O3 . Both properties can be achieved by a have, over the years, converted a part of their ca-
low degree of calcination. pacity to produce various alumina chemicals. In
fact, some of the older, smaller alumina refining
plants have been totally converted to alumina
5.2. Typical Specifications for chemicals production in order to be economi-
Metallurgical Alumina cally viable. Chemical uses account for nearly
8 % of the world production.
The considerations discussed in Section 5.1 have
contributed to the evolution of the general spec-
ifications used in production and international 6.1. Aluminum Hydroxides
trading (Table 8). These values are only rep-
resentative and considerable variation exists in Aluminum hydroxides constitute a versatile
actual practice depending on price, availability, group of industrial chemicals. Important uses
smelting practices, and many other factors. Con- requiring large quantities are as fillers in plas-
sistency of quality is a major consideration. tic and polymer systems and for the production
of aluminum chemicals. A moderate amount is
used for the production of alumina-based adsor-
Table 8. Typical properties of metallurgical alumina bents and catalysts.
Physical property Aluminum hydroxide meets most of the re-
quirements for an effective filler: white or near-
Particle size distribution, wt % white color; large volume production base, re-
+ 100 mesh (Tyler) <5
+ 325 (44 µm) > 92 sulting in price and supply stability; consistency
− 325 <8 of physical and chemical properties; a wide
Bulk density, kg/L
loose 0.95 – 1.00 range of particle size distributions; chemical in-
packed 1.05 – 1.10 ertness; and nontoxicity. However, its increas-
ing popularity as a plastics filler is strongly re-
Specific surface area, m2 /g 50 – 80
lated to its fire-retardant and smoke-suppressant
Moisture (to 573 K), wt % < 1.0 properties, which justify the somewhat higher
Loss on ignition (573 – 1473 K), < 1.0 price compared with calcium carbonate and
wt % other mineral fillers. Aluminum hydroxide acts
Attrition index (modified increase in < 44 µm particles
as a fire retardant by adsorbing heat through en-
Forsythe – Hertwig method) 4 – 15 wt % dothermic dehydration and dilution of pyrolyti-
cally produced combustion gas by the released
α-Al2 O3 content (by optical or < 20
X-ray method), % steam. Dehydration and water release processes
become significant at temperatures above 500 K.
Chemical analysis wt % The smoke-inhibiting activity of aluminum hy-
Fe2 O3 < 0.015
SiO2 < 0.015 droxide filler has been attributed to promotion
TiO2 < 0.004 of solid-phase charring in place of soot forma-
CaO < 0.040
Na2 O < 0.400 tion. Although offering these desirable features,
34 Aluminum Oxide

aluminum hydroxide has certain disadvantages range reflecting the cost of additional processing
that impose some limitations on its uses as a of the usual Bayer process product to suit ap-
filler. Like other nonreinforcing mineral fillers, it plication requirements. These include grinding,
generally lowers strength. Because it undergoes higher purity, classification, surface treatment,
thermal decomposition, it is not suitable for pro- etc. Pharmaceutical-grade gel hydroxides were
cessing above 500 K. These factors are respon- at the top of the price range.
sible for the larger use of aluminum hydroxide
in latex carpet backings and in glass-reinforced
polyesters, where processing temperatures be- 6.2. Adsorbent and Catalytic Aluminas
low about 480 K generally are used. These are
also chemically cross-linked or fiber-reinforced Activated aluminas represent another group of
systems, in which loss of strength caused by a technically important alumina chemicals. Prin-
nonreinforcing filler may not be very important. cipal uses are as drying agents, adsorbents, cat-
Aluminum hydroxide filler has been used less alysts, and catalyst carriers. These products are
extensively in thermoplastics, e.g., poly(vinyl obtained by thermal dehydration of different alu-
chloride) and polyethylene, and elastomeric ma- minum hydroxides in the 520 – 1070 K temper-
terials. For use as a filler, the crystalline alu- ature range (see Section 1.5).
minum hydroxide from the Bayer process is
dried and ground to particles
10 µm size. Spe-
cial grades with increased whiteness and a va- 6.2.1. Preparation of Activated Aluminas
riety of both particle size ranges and chemical
purity also are available commercially. Bayer aluminum hydroxide is the chief source
Fine, precipitated aluminum hydroxide hav- of commercial activated alumina products. Pow-
ing a uniform particle size (≈ 1 µm) is used in der forms of activated alumina are produced by
paper making as a filler pigment and as a coating. heating the hydroxide directly at 575 – 1825 K in
As a filler, it disperses rapidly with low sedimen- ovens or in rotary or fluidized-bed calciners. The
tation. Improved printing properties are reported products have surface areas of 200 – 350 m2 /g
for the hydroxide-filled paper. The application of and losses on ignition of 3 – 12 wt % (at
fine, platy aluminum hydroxide as a paper coat- 575 – 1473 K). Such products are used as de-
ing is well established in the paper industry. It colorizing agents for organic chemicals and as
gives a coating of high brightness, opacity, and starting material for the production of aluminum
gloss (→ Paper and Pulp). fluoride (→ Fluorine Compounds, Inorganic).
Technical aluminum hydroxide obtained Other uses include chromatographic and cat-
from the Bayer process is 99.5 % pure. It dis- alytic applications in organic chemistry.
solves readily in strong acids and bases. For Granular activated alumina produced from
these reasons, aluminum hydroxide is the pre- Bayer plant crust is one of the oldest commercial
ferred raw material for the production of a large forms of this product and still is used widely. A
number of aluminum compounds. These include flow sheet of the production process is shown in
pure, iron-free aluminum sulfate (used in the Figure 20. The activated material is a hard, non-
paper industry and for water purification), alu- dusting product. Table 9 lists some properties of
minum fluoride, synthetic zeolites, and sodium a commercial product of this type (Alcoa F-1).
aluminate. Aluminum hydroxide also is used in A similar granular product has been produced
the glass industry and in cosmetic and phar- by compacting Bayer hydroxide by mechanical
maceutical preparations. An important cosmetic pressure (Martinswerk GmbH, Federal Repub-
use of aluminum hydroxide is in toothpaste. The lic of Germany). The process utilizes a roll-type
mildly abrasive hydroxide cleans and polishes compactor. The product from the compactor is
teeth. broken up and sieved to the required size frac-
The price of aluminum hydroxides ranged tions and activated at 675 – 875 K in a rotary cal-
from $0.20 to $0.60 per kg in 1990, the price ciner.
 Aluminum Oxide 35
Table 9. Typical properties of Alcoa activated aluminas

F-1 H-151 S-100

Al2 O3 , % 92 90 95
Na2 O, % 0.58 1.6 0.35
SiO2 , % 0.12 2.0 0.03
Fe2 O3 , % 0.06 0.03 0.05
Loss on ignition, % 7 6 5
Loose bulk density:
g/cm3 0.83 0.82 0.80
lb/ft3 52 51 50
Packed bulk density:
3
g/cm 0.85 0.85 0.75
lb/ft3 55 53 47
Pore characteristics and surface area of typical Alcoa activated aluminas:
Helium (true) density, g/cm3 3.25 3.40 3.15
Mercury (particle) density, 1.42 1.38 1.24
3
g/cm
Micro pore volume (pores 0.017 0.023 0.012
< 3.5 nm), cm3 /g
Macro pore volume (pores 0.023 0.020 0.037
> 3.5 nm), cm3 /g
Total pore volume, cm3 /g 0.40 0.43 0.49
Total porosity, % 56.3 59.4 60.6
Pore diameter at 50 % total 17.7 3.5 4.7
pore volume, nm
Primary pore size range, nm 0 – 10000 0 – 40 0 – 500
BET surface area, m2 /g 250 360 260
Pore diameter, nm
6 7
10 – 10 0.0031 0.0003 0.0000
Pore volume, cm3 /g
5 6
10 – 10 0.0045 0.0001 0.0001
104 – 105 0.0059 0.0001 0.0004
103 – 104 0.0029 0.0004 0.0033
102 – 103 0.0045 0.0093 0.0047
2
35 – 10 0.0021 0.0099 0.0289
2 – 35 0.0165 0.0232 0.0115

0.0395 0.0433 0.0489

onds, has been used for the production of ball-

shaped, activated alumina having properties su-
perior to the granular product. This process re-
sults in the formation of nearly amorphous -
Al2 O3 . The product is finely ground and using
water as binder, formed into spherical agglomer-
ates in a rotating pan agglomerator. Rehydration
of -Al2 O3 with water leads to crystallization
of bayerite, causing the agglomerates to harden.
Reactivation of the hard balls at 675 – 775 K pro-
duces the activated product (5 – 20 mm in diam-
eter) having a surface area of 320 – 380 m2 /g.
Alumina gels also have been used for the
manufacture of activated aluminas. These gels
Figure 20. Flow sheet for production of activated alumina are produced by neutralization of aluminum sul-
from Bayer plant crust fate or ammonium alum by NH4 OH, or from
sodium aluminate by neutralization with acids,
Fast dehydration of Bayer aluminum hydrox- CO2 , NaHCO3 , and Al2 (SO4 )3 . The gelatinous
ide, either by vacuum or by exposure to high- aluminum hydroxide precipitate is filtered and
temperature gas (1050 – 1300 K) for a few sec- thoroughly washed and dried. The dried prod-
36 Aluminum Oxide

uct is activated, milled, and agglomerated to technical functions, such as gas and liquid dry-
a spherical product. Other forming processes, ing, water purification, and selective adsorption
such as extrusion, pelletizing, and tableting, also in the petroleum industry.
can be used. The product is finally activated Gases that have been dried successfully by
at 675 – 875 K to a loss on ignition value of alumina desiccants are:
about 6 %. Although gels of various textures acetylene cracked gas hydrogen oxygen
can be prepared, the usual industrial adsorbent air ethane hydrogen propane
products have very small pores (less than 4 nm chloride
ammonia ethylene hydrogen propene
in diameter) and surface areas in the range of sulfide
300 – 400 m2 /g. A flow sheet of a manufactur- argon freon methane sulfur dioxide
carbon dioxide furnace gas natural gas
ing process is shown in Figure 21. Table 9 re- chlorine helium nitrogen
ports data on a commercial, gel-based product
(Alcoa H-151).
In many applications an alumina desiccant can
dry gas to a lower dew point than any other com-
mercially available desiccant. The static water
adsorption capacities of two typical activated
aluminas (Alcoa F-1 and H-151) in contact with
air at different relative humidity conditions are
shown in Figure 22.

Figure 21. Production of gel-based activated alumina

Aluminum oxide hydroxide (boehmite), a by-

product from the Ziegler process for linear alco-
hol production, is another source of activated
alumina. The high purity of this material favors
its use in catalytic applications. The fine-particle
boehmite is normally extruded to various shapes.
The material is claimed to serve as its own binder
when peptized with glacial acetic acid. The ex-
trudate is cut to the required size, dried, and acti-
vated at 775 – 875 K. The surface area of the ac- Figure 22. Static water adsorption capacity of typical com-
tivated product is 185 – 250 m2 /g. Commercial mercial activated aluminas at 25 ◦ C (298 K)
bayerite also has been used to produce activated
alumina; the product is preferred in some cat- Moist gas usually is dried by passing it
alytic applications. through a column (or tower) packed with the
adsorbent. Adsorption of water on activated alu-
mina is strongly exothermic, releasing between
6.2.2. Adsorbent Applications 45 and 55 kJ of heat per mole of water adsorbed.
This factor must be considered in the design of
A major application of activated alumina is in the the drying tower. Both granular and spherical
field of adsorption, where its high surface area, forms of activated alumina can be used in desic-
pore structure, strength, and chemical inertness cant beds. Sizes from 2 to 20 mm are available
favor its use. The alumina performs important commercially. The granular products have lower
 Aluminum Oxide 37

surface areas and their application is based on 6.2.3. Catalytic Applications

low cost per kilogram, low water load, and low
stream pressure. Spherical products, produced Alumina is used in many industrial catalytic pro-
by either the gel or the fast dehydration pro- cesses, both as the catalyst and as a support
cesses, have larger surface areas, a narrower pore for catalytically active components. In many in-
structure, and a high adsorption capacity, and stances, the alumina support contributes to cat-
they are relatively more expensive than the gran- alytic activity and so assumes an essential role
ular variety. The spherical kind usually is spec- in the catalyst system. Other catalytic uses of
ified for high-pressure, high-moisture removal alumina take advantage of its strength, heat re-
duties. The alumina desiccant is regenerated by sistance, and inertness.
passing a current of hot, dry gas (475 K) through Although the common adsorbent aluminas
the bed, usually countercurrent to the main gas derived from Bayer hydroxide have many cat-
flow. alytic applications, high-purity materials (e.g.,
Liquids that can be dried with activated alu- boehmite from the Ziegler process for linear
mina include aromatic hydrocarbons, higher alcohol production) are sometimes preferred.
molecular mass alkanes, gasoline, kerosene, cy- Because of the lower cost of Bayer process-
clohexane, power system coolants, lubricants, based products, such techniques as water and
and many halogenated hydrocarbons. Liquids acid washing of the activated product have been
that are highly adsorbed on alumina (e.g., employed to reduce the alkali (Na2 O) content
ethanol and methanol), react or polymerize in of the Bayer material. The sodium oxide is
contact with activated alumina. Those contain- known to have a negative influence in many
ing components that tend to deposit on the alu- catalytic processes. Catalyst-forming methods
mina surface cannot be dried by activated alu- include tableting, pelletizing, compacting, ball
mina. Regeneration schemes for liquid dehydra- forming (agglomeration), and extrusion. Such
tion units are varied and depend on the liquid be- factors as purity, surface area, pore volume, and
ing dried. In some applications the liquid being size distribution, and rate of deactivation influ-
dried is vaporized, heated, and passed through ence catalyst performance and selectivity. In ad-
the desiccant bed to adsorb water. Hot, dry gases dition, crushing strength and resistance to attri-
also are used for regeneration. tion of the catalyst pellets are important con-
An evolving application of activated alumina siderations in practical operation of catalytic re-
is in water purification. Several important con- actors. Although these physical aspects of alu-
taminants have been removed from water suc- mina catalysts are well characterized, the sur-
cessfully and economically in pilot plants as well face structure and chemistry responsible for cat-
as in large-scale treatment plants. These include alytic activity still remains unclear. Many inves-
reduction of fluoride concentration in drinking tigators have attributed catalytic activity to the
water and in some industrial effluents, and re- intrinsic acidity of the surface of activated alu-
moval of color and odor from effluent water from mina. First, the combination of two neighbor-
dye works and paper mills. Removal of phos- ing OH− groups to form water during the dehy-
phate and arsenic also has been investigated. dration process leaves behind an exposed Al3+
Activated alumina can be used to separate one ion, which, because of its electron deficiency, be-
or more components from a gas or liquid stream haves as a Lewis acid site. In addition, hydroxyl
by taking advantage of differences in adsorp- groups are retained during thermal decomposi-
tion or desorption kinetics. For example, a short tion of aluminum hydroxide (see Section 1.5).
cycle process has been used to recover heavy These OH− ions on the surface may act as pro-
hydrocarbons from a stream of lighter hydro- ton donors (Brønsted acids). These Lewis and
carbons. Often a regeneration scheme can be Brønsted acid sites have been looked upon as the
devised that permits cyclic use of the alumina. active catalytic centers. Further “defect” struc-
In other instances, such as removal of catalyst tures are formed with increasing degree of de-
in polyethylene and hydrogen peroxide produc- hydration [56]. Of the types of defects created
tion, it is more economical not to recycle the during dehydration, those assumed to have the
alumina. greatest catalytic importance are the triplet va-
38 Aluminum Oxide

cancies. They provide unusual exposure of the Two different methods have been used com-
aluminum ions in the underlying layer and con- monly for preparation of alumina-supported cat-
stitute strong acid sites. alysts: impregnation and coprecipitation. The
Catalytic applications of alumina are exten- alumina support used in the impregnation pro-
sive. Important industrial processes employing cess generally has been formed into its final
alumina as a catalyst by itself include alco- shape (extrudates, tablets) prior to the impreg-
hol dehydration and the Claus process for sul- nation step. Impregnation with a salt solution of
fur recovery ( → Sulfur). Dehydration of alco- the active species is then carried out, followed
hols over activated alumina is one of the oldest by drying and thermal decomposition of the salt.
catalytic processes. Typical reaction conditions In the coprecipitation procedure, hydroxides of
for olefin production are 575 – 675 K and atmo- aluminum together with the active component
spheric pressure. Lower temperatures favor the are precipitated from a salt solution by neutral-
formation of ethers. The most suitable alumi- ization with ammonia or alkali. The washed pre-
nas for alcohol dehydration catalysis are those cipitate is dried, powdered, and processed (e.g.,
that have large surface areas (150 – 200 m2 /g) by extrusion) to the desired shape and finally
and possess good thermal and hydrothermal sta- activated by thermal dehydration. The coprecip-
bility. Coke formation occurs over a period of itation method is used when the active species
several hundred operating hours and the catalyst must be present in high concentrations or when
must be regenerated by burning off the carbon more uniform distribution of the active compo-
with hot air at 773 – 873 K. nent is desired.
The largest present-day catalytic application The technical and patent literature contains
of activated alumina itself is in the Claus process, innumerable examples of the use of alumina as
which is used to recover sulfur from hydrogen a catalyst support. Some important examples are
sulfide (H2 S). the catalytic dehydration of n-butane to butadi-
ene (used in synthetic rubber), using a chromia-
2 H2 S + SO2 → 2 H2 O + 3 S ∆H = − 147 kJ impregnated alumina catalyst; molybdenum –
alumina catalysts, used in hydrorefining opera-
The reaction is carried out catalytically in two tions (e.g., desulfurization) in petroleum refin-
or more conversion stages using alumina cat- ing; and pelleted catalysts containing platinum,
alysts. Reaction temperature in the first stage palladium, and rhodium on an alumina base,
is around 625 K. At this temperature, the con- used in automobile exhaust catalytic converters.
version of H2 S is only about 65 %. Subsequent United States production of adsorbent-grade
lower temperature catalytic stages are used to activated aluminas, both granular and spherical,
further reduce the H2 S concentration. Spheri- amounted to nearly 250 000 t in 1990. Price of
cal, high-strength activated alumina catalysts are the cheaper, granular product was quoted around
used in the Claus converters. Service life as high $ 0.40 – 0.50 per kg. Price of the spherical prod-
as 5 years has been reported. Deactivation of the uct ranged from $ 0.55 to $0.65 per kg. Total
alumina catalyst occurs by sulfation, thermal ag- catalytic applications of alumina in the United
ing, and carbon and/or sulfur deposition. Regen- States were estimated to be around 400 000 t in
eration of Claus catalyst involves removal of sul- 1990. Price of preformed alumina for catalytic
fur and burning off of carbon deposits. applications ranges from $ 0.60 to $ 4.00 per kg,
Alumina-supported catalysts are used exten- depending on source and purity. Alumina-based
sively in the petroleum and chemical industries. Claus catalyst was priced between $ 3.00 and
In general, the petroleum industry catalysts have $ 3.50 per kg.
high surface area and high porosity; the sup-
port is mostly activated alumina. On the other
hand, many typical chemical process catalysts 7. Ceramic Uses of Alumina
(e.g., ammonia synthesis, steam reforming) are
characterized by lower surface area (< 20 m2 /g) Alumina is used extensively as a ceramic ma-
and are nonporous or have very large diameter terial (→ Ceramics, Advanced Structural Prod-
pores. The carrier in this case is inert and consists ucts). Products range from relatively low-
mostly of calcined or sintered alumina products. calcined grades of polishing aluminas to the
 Aluminum Oxide 39

extremely hard, fused alumina and syntheti- 8. Toxicology and Industrial Hygiene
cally produced sapphire. The characteristics that
make alumina valuable in ceramic applications For a discussion concerning the toxicology
are high melting point (2325 K), hardness (9 on and industrial hygiene of aluminum oxides,
the Mohs scale), strength, dimensional stabil- → Aluminum, Chap. 9.
ity, chemical inertness, and electrical insulating
ability. These, together with availability in large
quantities at moderate prices, have led to exten- 9. References
sive and varied uses of alumina as a ceramic
material. General References
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Aluminium, Teil 1, Die Tonerde, W. De
7.1. Calcined Alumina Gruyter, Berlin 1964.
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There are two general types: those having about Editions Eyrolles, Paris 1964.
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< 0.1 %. Principles of Bayer Process Design, Extractive
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Amalgams → Mercury, Mercury Alloys, and Mercury Compounds

Americium → Transuranium Elements
Amidosulfuric Acid → Sulfamic Acid
Amine Oxides → Surfactants