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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
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1. General Aspects
Almost 4000 years ago Egyptians and Babylonians used aluminum compounds in various chemicals
and medicines. HERODOTUS mentioned alum in the fifth century B.C. and PLINY referred to "alumen," now
known as alum, as a mordant to fix dyes to textiles around 80 A.D. In 1754 MARGGRAF showed that a
distinct compound existed in both alum and clays. In 1761 the French chemist GUYTON DE MORVEAU
proposed the name "alumine" for the base in alum, identified in 1787 by ANTOINE LAVOSIER as the oxide
of a then-undiscovered element. By the 1700s the earthy base alumina was recognized as the potential
source of a metallic element.
GREVILLE (1798) described a mineral from India that had the composition Al
2
O
3
and named it corundum
[1302-74-5], derived from the native name of this stone. HAY (1801) called a mineral diaspore [14457-
84-2] (from the Greek "diaspora" meaning dispersion) because it decrepitated on heating. Its
composition, Al
2
O
3
H
2
O, was determined by VAQUELIN in 1802. Gibbsite [14762-49-3], named after
the American mineralogist G. GIBBS, was found by DEWEY in 1820; TORREY (1822) showed this mineral to
have the composition Al
2
O
3
3 H
2
O. The name hydrargillite [14762-49-3] was given to a similar
mineral found later in the Ural Mountains. Using the newly developed technique of X-ray diffraction,
BHM and NICLASSEN [13] identified a crystalline aluminum oxide hydroxide, Al
2
O
3
H
2
O, later named
bhmite (boehmite). BHM discovered a second type of trihydroxide, Al
2
O
3
3 H
2
O, a year later. FRICKE
[14] suggested the name bayerite [20257-20-9] for this compound, believing it to be the product of the
Bayer process, which he later identified as gibbsite. Only few occurrences of natural bayerite have been
reported [15]. VAN NORDSTRAND et al. [16] reported a third form of trihydroxide, which was later named
nordstrandite [13840-05-6] in his honor.
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1.1. Aluminum Hydroxides
A general classification of the various modifications of aluminum hydroxides is shown in Figure (1).
The best defined crystalline forms are the three trihydroxides, Al(OH)
3
: gibbsite, bayerite, and
nordstrandite, and two modifications of aluminum oxide hydroxide, AlO(OH): boehmite and diaspore.
Besides these well-defined crystalline phases, several other forms have been described 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]. Mineralogic and structural data are listed in Tables (1) and (2).
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Gelatinous hydroxides may consist of predominantly X-ray indifferent aluminum hydroxide or
pseudoboehmite. The X-ray diffraction pattern of the latter shows broad bands that coincide with
strong reflections of the well-crystallized oxide hydroxide boehmite.
The aluminum hydroxides found abundantly in nature are gibbsite, boehmite, and diaspore. Gibbsite
and bayerite have similar structures. Their lattices are built of layers of anion octahedra in which
aluminum occupies two thirds of the octahedral interstices. In the gibbsite structure, the layers are
somewhat displaced relative to one another in the direction of the a axis. The hexagonal symmetry of
this lattice type (brucite type) is lowered to monoclinic. Triclinic symmetry was found in larger gibbsite
single crystals from the Ural Mountains [17].
In bayerite the layers are arranged in approximately hexagonal close packing. Because of shorter
distances between the layers, the density is higher than in the case of gibbsite. The crystal class and
space group of bayerite have not yet been established clearly.
The individual layers of hydroxyl ion octahedra in both the gibbsite and the bayerite structures are
linked to one another only through weak hydrogen bonds. Bayerite does not form large single crystals.
The most commonly observed growth forms are spindle- or hourglass-shaped somatoids. The long axis
of these somatoids stands normal to the basal plane; i.e., the somatoids consist of stacks of Al(OH)
3

layers (Fig. (2)). The effect of alkali ions on the structures of Al(OH)
3
types was investigated by
several workers [3], [18], [19]. Intercalation of Li
+
ions transforms gibbsite to the hydrotalcite structure
[20].
Gibbsite crystals of appreciable size are not uncommon. Clear pseudohexagonal platelets about 1 mm
in diameter are known from Ar in Norway. Prismatic crystals 0.51 mm in length are occasionally
produced in the Bayer process.
Nordstrandite, the third form of Al(OH)
3
, was described by VAN NORDSTRAND [16] and others [21]. The
structures of nordstrandite and bayerite were investigated [22] and compared with those of monoclinic
and triclinic gibbsite, which had been determined previously [17].
The lattice of nordstrandite is built of the same, electrically neutral Al(OH)
3
octahedral layers that form
the structural elements of gibbsite and bayerite [14]. The lattice period amounts to 1.911 nm in the
direction normal to the layer. This corresponds to the sum of identical layer distances of bayerite plus
gibbsite. The identical nordstrandite structure consists of alternating double layers, in which the OH
octahedra are arranged once in the packing sequence of bayerite, and then in that of gibbsite. Material
containing continuous transitions from bayerite through nordstrandite to gibbsite has been prepared
through the proper selection of precipitation conditions [18].
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1.2. Aluminum Oxide Hydroxides
Pseudoboehmite is formed during aging of X-ray indifferent hydroxide gels as a precursor of
trihydroxide. The reflections of pseudoboehmite are broadened not only because of the very small
particle size, but also because of variable distances of the AlO(OH) double chains, which form the
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
structural element of pseudoboehmite as well as of well-crystallized boehmite. The lattice spacing in
the direction of the c axis increases by 0.117 nm for each mole of excess water [22].
Boehmite consists of O, OH double layers in which the anions are in cubic packing. The aluminum ions
are octahedrically coordinated. These layers are composed of chains of [AlO(OH)]
2
extending in the
direction of the a axis [23]. The double layers are linked by hydrogen bonds between hydroxyl ions in
adjacent planes. Boehmite crystals exhibit perfect cleavage parallel to the (010) plane.
In the diaspore structure the oxygen ions are nearly equivalent, each being joined to another oxygen
center through a hydrogen ion. The anions are hexagonally close packed [24]. The position of the
hydrogen ion has been established by neutron diffraction [25]. The OHO distance is 0.265 nm. By
infrared studies, the bond energy for the hydrogen bridges in diaspore was determined to be 28.7
kJ /mol, compared with 20.1 kJ /mol for boehmite [26].
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1.3. Aluminum Oxide, Corundum
The hexagonally closest packed o-Al
2
O
3
modification is the only stable oxide in the Al
2
O
3
H
2
O
system. Corundum is a common mineral in igneous and metamorphic rocks. Red and blue varieties of
gem quality are called ruby and sapphire, respectively. The lattice of corundum is composed of
hexagonally closest packed oxygen ions forming layers parallel to the (0001) plane. Only two-thirds of
the octahedral interstices are occupied by aluminum ions. The structure may be described roughly as
consisting of alternating layers of Al and O ions. The corundum structure was determined in the early
1920s [27]; numerous workers later confirmed and refined these data [3]. Properties of corundum are
listed in Tables (1) and (2).
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1.4. The Al
2
O
3
H
2
O System
Under the equilibrium vapor pressure of water, crystalline Al(OH)
3
converts to AlO(OH) at about 375
K. The conversion temperature appears to be the same for all three forms of Al(OH)
3
. At temperatures
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
lower than 575 K, boehmite is the prevailing AlO(OH) modification, unless diaspore seed is present.
Spontaneous nucleation of diaspore requires temperatures in excess of 575 K and pressures higher than
20 MPa. In the older literature, therefore, diaspore was considered the high-temperature form of
AlO(OH). The first reaction diagram of the phase transitions in the Al
2
O
3
H
2
O system was published
in 1943 [28]. These workers determined the gibbsite boehmite conversion temperature to be 428 K.
Boehmite transformed to diaspore above 550 K; diaspore converted to corundum, o-Al
2
O
3
, at 725 K.
Similar results were reported in 1951 [29].
The system was reinvestigated in 1959 [30] and in 1965 [31]. A phase diagram based on these data is
shown in Figure (3). Diaspore is the stable modification of AlO(OH); boehmite is considered
metastable, although it is kinetically favored at lower temperatures and pressures. This is because the
nucleation energy is lower for boehmite than for the considerably more dense diaspore. Nucleation is
additionally facilitated by the possibility that boehmite can grow epitaxially on Al(OH)
3
. In the Al
2
O
3

Fe
2
O
3
H
2
O system, the presence of the isostructural goethite, o-FeO(OH), lowers the nucleation
energy for diaspore so that this AlO(OH) modification crystallizes at temperatures near 373 K [32].
This observation explains the occurrence of diaspore in clays and bauxite deposits that have never been
subjected to high temperatures or pressures.
Nomenclature. Although there is fairly good agreement in the more recent literature on phase fields
and structures of the crystalline phases in the Al
2
O
3
H
2
O system, the nomenclature is still rather
unsystematic.
Bayerite, gibbsite (hydrargillite), and nordstrandite are trihydroxides of aluminum, and not oxide
hydrates. The designation "aluminum oxide monohydrate" for boehmite and diaspore is also incorrect.
Both are true oxide hydroxides. Molecular water has been determined only in poorly crystallized,
nonstoichiometric pseudoboehmite.
The designation of the modifications of aluminum hydroxides and oxides lacks uniformity just as much
as does the nomenclature of the compounds. According to the general usage in crystallography, the
most densely packed structures are designated as o-modifications [3]. Bayerite, diaspore, and
corundum fall within this class. The compounds with cubic packing sequence, gibbsite and boehmite,
have been designated by the symbol . Nordstrandite can be classified as |-Al(OH)
3
when regarding
this compound not as an intergrowth of bayerite and gibbsite, but as an independent modification.
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1.5. Thermal Decomposition of Aluminum Hydroxides
When aluminum hydroxides or oxide hydroxides are heated in air at atmospheric pressure, they
undergo a series of compositional and structural changes before ultimately being converted to o-Al
2
O
3
.
These thermal transformations are topotactic. Despite a loss of 34 or 15% of mass for the trihydroxides
or oxide hydroxides, respectively, the habit of the primary crystals and crystal aggregates changes very
little. This leads to considerable internal porosity, which may increase the specific surface area of the
material to several hundred m
2
/g. Structural forms develop that, although not thermodynamically
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
stable, are well reproducible and characteristic for a given temperature range and starting material.
These transition aluminas have been the subject of numerous investigations because of their surface
activity, sorptive capacity, and usefulness in heterogeneous catalysis. The literature in this field of
physical chemistry has been reviewed up to 1987 [3].
The simplest transformation is that of diaspore to corundum. As the structures of these two compounds
are very similar, the nucleation of o-Al
2
O
3
requires only minor rearrangement of the oxygen lattice
after the hydrogen bonds are broken. A temperature below 860870 K is sufficient for complete
conversion. The newly formed corundum grows epitaxially on the decomposing diaspore, with the
(0001) plane of Al
2
O
3
parallel to the (010) plane of AlO(OH) [33]. Recent work [34] has shown that
transformation to corundum (o-Al
2
O
3
) proceeds through an intermediate o'-Al
2
O
3
phase.
The thermal transformation, at ambient pressure, of boehmite and the trihydroxides to o-Al
2
O
3
requires
considerably more structural rearrangements and is generally not completed until the temperature
reaches at least 13751400 K. The first step in the reaction sequence is the diffusion of protons to
adjacent OH groups and the subsequent formation of water [35], [36]. This process begins at a
temperature near 475 K. If this water cannot diffuse rapidly out of larger trihydroxide particles,
hydrothermal conditions may develop locally, resulting in the formation of -AlO(OH). With
increasing loss of water, a large internal porosity develops. The lattice voids left by the escaping water
are not readily healed because of the slow diffusion 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 crystalline 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)). 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, furnace 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.
Transition oxides formed at lower temperatures are mostly two-dimensional, short-range ordered
domains within the texture of the decomposed hydroxides. Extensive three-dimensional ordering
begins at about 1050 K. Until completely converted to corundum, the solid retains considerable
amounts of OH

ions. Most likely protons are retained to maintain electroneutrality in areas deficient of
cations. Therefore, the presence of protons may retard the reordering of the cation sublattice. The high
surface area (>75 m
2
/g) of -Al
2
O
3
has been shown to provide thermodynamic stability [37]. Addition
of fluorine to the furnace atmosphere removes protons. As a result, rapid transition to o-Al
2
O
3
occurs
at temperatures as low as 1150 K. Markedly tabular corundum crystals form, possibly because the
preceding transition alumina is mostly two-dimensionally ordered [38].
Transition forms other than those shown in Figure (6) can be obtained by hydrothermal treatment [3].
The structures of various transition forms have been investigated [17], [22], [39].
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
1.6. Aluminates and Related Compounds
Sodium oxide forms several compounds with aluminum oxide. These so-called |-aluminas represent a
group of aluminates having the same, or very similar, structures but variable chemical composition.
Their molar ratios (Na
2
O:Al
2
O
3
) can vary between 1:1 and 1:11. The 1:1 sodium aluminate, NaAlO
2

[1302-42-7], exists in at least two allotropic modifications. Orthorhombic |-NaAlO
2
is stable below
750 K; the higher temperature modification is tetragonal. For preparation and properties of technical
sodium aluminate, Aluminum Compounds, Inorganic - 2.1. Sodium Aluminate.
The 1:11 |-Al
2
O
3
crystallizes from melts containing aluminum oxide and sodium oxide or other
sodium compounds. A 1:5 |-alumina has been prepared by heating o-Al
2
O
3
with NaAlO
2
or Na
2
CO
3

at about 1325 K.
Several other |-aluminas containing CaO, BaO, or SrO in 1:6 ratio also have been reported [3].
Recent interest in |-alumina is related to its use as a solid electrolyte in sodiumsulfur secondary
batteries ( Batteries).
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2. Bauxite, the Principal Raw Material
2.1. Definition and Geology
The term bauxite [1318-16-7] is used for sedimentary rocks that contain economically recoverable
quantities of the aluminum minerals gibbsite, boehmite, and diaspore. The name derives from the
description by BERTHIER, in 1821, of a sediment that occurred near the village of Les Baux in the
Provence, France. Originally assumed to be a dihydrate of aluminum oxide, bauxite was later
recognized as being composed of aluminum hydroxide, iron oxide and hydroxide, titanium dioxide, and
aluminosilicate minerals [2].
Early in this century, major bauxite deposits were found in various parts of the Tertiary and Cretaceous
limestone formations of the European Alps; also in several locations on the North American continent,
e.g., in Arkansas, Alabama, and Georgia. Since the 1920s, extensive deposits have been discovered in
the tropical and subtropical climate belts.
The oldest known bauxites developed in the Precambrian; the youngest are of recent origin. Deposits
may occur as extensive, flat bodies blanketing areas of many square miles; they may form irregularly
shaped fillings of dolinas in old karst surfaces, or lenses several hundred meters in diameter and tens of
meters thick. Allochtonous, i.e., displaced bauxites, are also common; erosion of primary deposits and
redeposition of the detritus in valleys or along mountain slopes has frequently led to mineable
accumulations of ore.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Many of the geologically younger bauxites are covered only by thin layers of soil; others are buried by
coastal or alluvial sediments. Older deposits, especially in the Balkans or the Ural Mountains, often are
overlain by carbonate rocks hundreds of meters thick. Regardless of their geologic age, all bauxites
were formed during continental periods [40].
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2.2. Composition and Properties
The chemical composition of bauxites of various origin is given in Table (3) [2]. Aluminum oxide, iron
oxide, and titanium and silicon dioxides are the major chemical components of all bauxites. Alkali and
alkaline earth compounds are rarely found.
Gibbsite, -Al(OH)
3
, is the predominant aluminum mineral in the geologically young bauxites of the
tropical climate belt. Mesozoic and older bauxite contain mostly boehmite (-AlO(OH)) or diaspore (o-
AlO(OH)). Since their formation, many of the older bauxites have been buried under considerable
layers of younger sediments and often were subjected to tectonic stress. Boehmite and diaspore
formation appears to be related to an increasing degree of metamorphism. However, both minerals also
occur in young deposits, although in minor quantities. The chemical environment obviously plays as
important a role in the formation of boehmite and diaspore as do pressure and stress [40].
Dissolution of gibbsite requires the mildest conditions in the Bayer process (see Section 3.1.2.
Digestion). Higher temperatures and alkali concentrations are necessary for the digestion of boehmite
and diaspore. Technically, both oxide hydroxides can be processed without difficulties. The current
abundance of high-grade gibbsitic bauxites, however, has made boehmite- and diaspore-rich ores
economically less attractive.
Goethite, o-FeO(OH) [1310-14-1], and hematite, o-Fe
2
O
3
[1309-37-1], are the most prevalent iron
minerals in bauxites. They are practically inert under the conditions of the Bayer process. In both
materials, some of the iron may be replaced isomorphically by aluminum ions. This amount of
aluminum is included in the chemical analysis of the bauxite but is normally not extracted in the digest.
Magnetite (Fe
3
O
4
) is found in some European bauxites; pyrite (FeS
2
) and siderite (FeCO
3
) also may
occur. Decomposition of pyrite may lead to high sulfur levels in the process solutions.
Anatase, TiO
2
[1317-70-0], is the titanium mineral found most frequently in bauxites. Rutile, TiO
2

[1317-80-2], occurs in some European deposits; FeTiO
3
is also present in minor quantities, especially
in titanium-rich bauxites. Titanium dioxide minerals are attacked under only the most severe conditions
of the Bayer process.
Silicon dioxide may occur as quartz [14808-60-7], as in the bauxites of the Darling Range in Western
Australia. Most commonly, however, SiO
2
is associated with the clay minerals kaolinite, halloysite, or
montmorillonite. These aluminosilicates react with sodium aluminate solutions to form insoluble
sodium aluminum silicates during digest, causing loss of sodium hydroxide and extractable alumina.
The amount of so-called reactive silica is one of the major factors determining quality and price of the
ore.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Minor constituents, such as chromium, vanadium, zinc, and gallium, have little effect on the Bayer
process or on the quality of the final product. Some tend to accumulate in the recirculated process
solutions (e.g., gallium and vanadium) and must be removed periodically by appropriate treatments.
The physical properties of bauxites, i.e., texture, hardness, and density, can vary widely. Geologically
old diaspore bauxites, especially those high in iron oxide, are very hard and can reach densities of 3.6
g/cm
3
. Young tropical deposits, in contrast, may have an earthy, soft texture and a density around 2.0
2.5 g/cm
3
. Allochtonous bauxite often consists of hard nodules embedded in a soft, usually clayey
matrix. Porous textures also occur. The color of bauxites is largely determined by the type and particle
size of the prevalent iron mineral. Highly dispersed goethite tends to be yellow to orange, whereas dark
brown tones usually are associated with coarser hematite. Colors can vary greatly within a single ore
body.
Hardness, texture, and the amount of overburden determine the methods applied for bauxite mining.
Deposits in Greece, former Yugoslavia, Hungary, and the former Soviet Union require deep mining to
depths of several hundred meters, often complicated by the difficulties of controlling water levels in
the porous limestone formations. Tropical bauxites frequently are located so close to the surface that
they can be recovered with normal earth-moving equipment.
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2.3. Genesis of Bauxites
Many of the geologically young bauxite deposits are located in the savannah region, which extends
north and south of the tropical rain forest belt. The climate of this region is characterized by a high
mean annual temperature and abundant precipitation during the rainy season. Deposits occur on gently
sloping hills or on peneplains. The stratigraphic evidence shows that these bauxites have formed in situ.
Parent rocks may be coarse-grained, igneous rocks such as syenite, phonolite, basalt, or gabbro.
However, large deposits also developed on kaolinitic sandstones, on phyllites, and on schists. A layer
of kaolinitic clay is frequently found between the ore body and the parent rock.
Bauxite probably forms during long periods of low geologic activity when the combination of high
temperature, abundant precipitation, and good vertical drainage favors intensive chemical weathering.
The sequence of leaching begins with removal of alkali followed by the removal of alkaline earths.
Oxides of iron, aluminum, titanium, and silicon are mobilized and reprecipitated as hydroxides and
oxides. Aluminum hydroxide and silica form kaolinite, Al
4
(OH)
8
Si
4
O
10
. This sequence first leads to
the formation of tropical soils (laterites). Bauxitization follows when the climatic, chemical, and
topographic conditions prevail long enough to allow the removal of silicon dioxide as well.
The bauxite deposits of the Mediterranean region, the Caribbean Islands, and many other locations that
are associated with tertiary and older limestone formations (karst bauxites) were formed by a similar
weathering process. Parent materials were lateritic soils and clays transported into the karst region and
deposited in depressions. During extended terrestrial periods, high mean temperatures, copious
precipitation, and good vertical draining through the porous limestone bedrock facilitated a thorough
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
desilification. In the older literature, the parent material for karst bauxitization was reported to be
clayey residue left after weathering of substantial layers of carbonate rocks [41]. Researchers have
shown conclusively that igneous rocks were the source of this material [42][43][44].
Comprehensive reviews on the geology, mineralogy, and genesis of bauxites have been published [40],
[45].
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2.4. Major Bauxite Deposits
Until the 1950s, the European aluminum industry was supplied from the karst bauxite deposits of
France, Hungary, former Yugoslavia, and Greece. United States sources (Arkansas) and ore from
Surinam provided the raw material for North American production. Since then, the picture has changed
dramatically. The four largest bauxite producers of 1990, namely, Australia, Guinea, J amaica, and
Brazil (Table (4)), hardly would have been mentioned in 1950. Today, they provide more than half of
the world's total bauxite output.
Africa. The Savannah region covers an area of the African continent that has experienced low geologic
activity for a long time. In this belt, which stretches from the Ivory Coast to Madagascar, very large
bauxite deposits were found. The major production is currently concentrated in Guinea and Ghana.
Cameroon, Sierra Leone, Mali, and the Congo region, among other areas, have substantial reserves.
Australia. Major deposits are located in the Darling Range in Western Australia, on the Gove Peninsula
in the Northern Territory, and on the Cape York Peninsula in Queensland. Bauxite also occurs in New
South Wales, in Victoria, and on the island of Tasmania. The Australian deposits developed between
the Eocene and Pliocene epochs on substrates ranging from Precambrian sandstones to Tertiary basalts.
Gibbsite is the predominant aluminum mineral, although some boehmite occurs in all but the Western
Australian deposits.
South America. On the outer slopes of the old Guyana Shield, many economically important deposits
have been found. They are located in the Amazon Basin of Brazil, in Colombia, Venezuela, Surinam,
Guyana, and French Guyana. Surinam and Guyana have been producing for more than 60 years,
whereas the Brazilian Amazon deposits have been mined only recently. Bauxite also is produced in the
Pocos de Caldas area in Southern Brazil, state of Minas Gerais. The South American bauxites generally
are geologically young, gibbsitic ores.
Caribbean. J amaica and the Dominican Republic have major reserves of karst bauxites that occur on
Tertiary limestones under generally very thin overburden. Although gibbsite is the main aluminum
mineral, some boehmite also is present. J amaica has been one of the world's leading bauxite producers
for the past 20 years.
North America. The only economically important deposit is located in Arkansas, where gibbsitic
bauxite developed on nepheline syenite during the Eocene. Less than 5 10
7
t of bauxite remain, and
the grade is declining.
Europe. Except for a few commercially insignificant occurrences, all European bauxites are of the karst
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
type. The oldest deposits (Devonian/Mississippian) are those of the Tikhvin area in the former Soviet
Union; the youngest are the Eocene bauxites of former Yugoslavia. Most European deposits developed
during the Lower and Upper Cretaceous, e.g., the diaspore and boehmite bauxites of France, Greece,
and Romania, and the gibbsite and boehmite bauxites found in Hungary, former Yugoslavia, and Italy.
Today, all European mines combined contribute only about 15% of world production.
Asia. Major deposits of gibbsite bauxites occur in India; the island of Kalimantan (Indonesia) has large
potential reserves. Numerous bauxite deposits, most of them containing geologically old, diaspore-rich
ore, were found in China. Substantial deposits also are located in Western Siberia.
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References
2.5. Economic Aspects
The proved reserves of bauxite shown in Table (4) are sufficient to supply the world aluminum industry
for a few centuries. Total resources are estimated by the U.S. Geological Survey at 55 to 75 10
9
t.
Because of the worldwide distribution of significant ore deposits, a disruption of bauxite supply for
political reasons appears highly unlikely. In 1974 several major bauxite-producing nations formed the
International Bauxite Association (IBA) with the intent of increasing control over the exploitation of
their bauxite deposits. Although levies were increased substantially, competition from countries not
associated with the IBA helped maintain a reasonable price structure.
Dissolution of gibbsite requires the mildest conditions in the Bayer process (see Section 3.1.2.
Digestion). Higher temperatures and alkali concentrations are necessary for the digestion of boehmite
and diaspore. Technically, both oxide hydroxides can be processed without difficulty. The current
abundance of high-grade gibbsitic bauxites, however, has made boehmite- and diaspore-rich ores
economically less attractive.
Economic and political considerations currently favor refining of bauxite near the deposit and shipment
of either alumina or aluminum ingot. Brazil, Surinam, and Australia have smelters, although their
refining capacity by far exceeds the demands of domestic metal production. J amaica and Guinea refine
a substantial portion of their own bauxite production.
About 25% of all bauxite mined is used for producing refractories, abrasives, catalysts, adsorbents, and
other industrial chemicals.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
References
3. Bayer Process
3.1. History and Procedure
In 1855 the French mining engineer LOUIS LE CHATELIER obtained alumina from bauxite by sintering with
sodium carbonate at 1200 C and leaching the sodium aluminate with water. Aluminum hydroxide was
then precipitated from the sodium aluminate solution by carbon dioxide. Early use of aluminum
hydroxide was chiefly as a mordant in the textile dyeing industry. The demand for pure alumina
increased rapidly when it became the raw material for aluminum production upon development of the
HallHroult cell. The Austrian chemist KARL J OSEPH BAYER received German patent 43977 in August,
1888 for a new, improved process for production of aluminum hydroxide from bauxite, and the process
became known as the Bayer process in his honor. Bayer initially worked on his process at the Tentelev
chemical plant near St. Petersburg in Russia. Between 1888 and 1900 he supervised the construction of
Bayer process plants in Germany, England, France, Italy, and the United States. The Merrimac
Chemical Company in Massachusetts first used the Bayer process in the United States, and the Alcoa
plant in East St. Louis, Illinois, was constructed in 1901. Since then, plants have been built in more
than 25 countries, and the present world alumina capacity is over 40 10
6
t/a (Table (5)).
The important features exploited in the Bayer process are that boehmite, gibbsite, and diaspore can be
dissolved in NaOH solutions under moderate hydrothermal conditions; the solubility of Al
2
O
3
in NaOH
is temperature dependent; most other components of the bauxite are quite inert in the process; and the
silica that does dissolve subsequently forms a nearly insoluble compound. These features permit
formation of a sodium aluminate solution, physical separation of the impurities, and precipitation of
pure Al(OH)
3
from the cooled solution.
The main features of the Bayer process have remained unchanged for the last 100 years, although the
scale of operations has been enlarged considerably due to chemical engineering developments. Figure
(7) shows the flow sheet of the process as it is now practiced.
Each operation in the process is carried out in a variety of ways. The process begins with preparation of
the bauxite by blending for uniform composition followed by grinding. In most plants the bauxite is
ground while suspended in a portion of the process solution. This slurry is mixed with the balance of
the heated NaOH solution, then treated in a digester vessel at well above atmospheric pressure. The
digest reaction is:
Al(OH)
3
+Na
+
+OH

Na
+
+Al(OH)
4

Additional reactions convert impurities such as SiO


2
, P
2
O
5
, and CO
2
to relatively insoluble
compounds. The slurry leaves the digester at a temperature above its atmospheric boiling point and is
cooled by flashing off steam as the pressure is reduced in several stages. The flashed steam is used to
heat the slurry and the solution going to the digester. The bauxite residue solids are separated from the
sodium aluminate solution in two steps so that the coarse fraction is processed separately from the fine.
Both residue fractions are washed and discarded. The solution, being free of solids, is cooled and
seeded with fine crystals of Al(OH)
3
; this causes the Al(OH)
4

ions to decompose to Al(OH)


3
, thereby
reversing the reaction that previously had taken place in the digester. Again, the heat removed in
cooling the solution is used to heat a colder stream in the process. After the precipitation reaction has
proceeded to the point that about half of the Al
2
O
3
in the solution has been removed, the mixture of
solids and solution is sent to classifiers. The fine Al(OH)
3
particles are returned to the process to serve
as seed. The coarse particles are washed and calcined to Al
2
O
3
. Excess solution introduced in washing
the product and the residue must be removed by evaporation. In some cases the solution is treated to
remove both organic and inorganic impurities before the solution is recycled through the plant.
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3.1.1. Bauxite Preparation
The bauxite entering the refinery must be uniform and sufficiently fine that extraction of the Al
2
O
3
and
the other operations are successful. The chemical composition of bauxite varies. Uniformity is
improved by blending material mined from several pits and, if necessary, by adding bauxite from
storage piles. A more recent development is to store ground bauxite slurry in surge tanks before it is
pumped to digestion. These agitated tanks are operated so that plant feed is uniformly blended for
several hours. Sometimes bauxites are dried to improve handling or washed to remove clay.
Hard bauxite is reduced to particles finer than 2 cm in roll or cone crushers and hammermills. Before it
enters the process it is ground further to less than 0.15 cm.
Previously, fine grinding was done in dry mills operating in closed circuit with vibrating screens. Such
operation required very dry bauxite to avoid blinding the screens. This resulted in a dusty working
environment. In most modern plants, the bauxite is mixed with a portion of the process solution and is
ground as a slurry. Rod mills and ball mills are used most frequently. The ground slurry may be passed
over screens or through cyclones, with the fine particles progressing and the coarse ones being returned
to the mills.
In all-wet grinding the bauxite feed and the flow of solution are controlled to keep the solids content of
the slurry between 45 and 55%. The power consumed by the mill drive is an indicator of the amount of
grinding being done and may be used to control the feed to the mill. On a longer time scale the particle
size of the product can be used to make changes in the grinding operation.
3.1.2. Digestion
In digestion, all of the Al
2
O
3
in the bauxite must be extracted. A solution is produced that contains the
maximum Al
2
O
3
concentration that can remain stable through the rest of the process. This must be
accomplished while using a minimum amount of energy.
The conditions for digestion can and do vary widely. The first consideration is whether the available
Al
2
O
3
is present as gibbsite, boehmite, diaspore, or a mixture of these minerals. The dissolution rates of
the three are quite different. Generally, if the bauxite contains mixed phases, the digestion conditions
will be chosen on the basis of the least soluble compound. Any Al(OH)
3
or AlOOH left undissolved
can act as seed in the clarification step, causing precipitation of Al(OH)
3
while the residue is still in
contact with the solution. In the sweetening process, boehmitic bauxite is digested under relatively mild
conditions, producing an intermediate Al
2
O
3
concentration. In a separate vessel, gibbsitic bauxite is
added to the flow from the first digest to raise the Al
2
O
3
concentration to the desired level. Another
approach is to digest only the gibbsite in a mixed bauxite. The residue is separated from the solution
and redigested under more severe conditions to recover the boehmite. This method reduces the flow to
the high-temperature digest and so requires lower capital and operating costs.
The solubility data (Fig. (8)) show that the Al
2
O
3
concentration in the process solution can be increased
by increasing the temperature, the NaOH concentration, or both [1][2][3][4]. As a result, operating
conditions in plants vary widely. Higher digest temperatures result in higher pressures, making the
equipment more expensive. There also is the need for more heat-exchange 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. Precipitation is thought to occur better at
lower concentrations, but use of low precipitation concentrations while digesting at high concentrations
requires dilution and additional operating costs for subsequent evaporation. Choosing digester
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conditions involves balancing these physical factors with local economics, together with the designer's
experience. This has resulted in the spectrum of operating conditions given in Table (6).
The conditions listed in the first line of Table (6) are those for digesting bauxite at the atmospheric
boiling point. Quite high alkali concentrations are required and the evaporation requirement is an
extraordinary 5.3 t of water for a tonne of Al
2
O
3
. 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 European 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; therefore, a higher temperature was required.
The second important reaction in digestion is desilication. In the equation below, kaolinite (1) is used
to illustrate the reaction of siliceous minerals with the process solution:
Al
2
O
3
2SiO
2
2H
2
O +6NaOH 2NaAlO
2
+2Na
2
SiO
3
+5H
2
O
The soluble products react to form a series of precipitates with zeolite structure, having a composition
of approximately Na
8
Al
6
Si
6
O
24
(OH)
2
.
Depending on temperature and concentration, the ratio of Al
2
O
3
:SiO
2
in the zeolite (tectosilicate)
structure can vary. For each Al
3+
replacing Si
4+
in the lattice, one Na
+
is taken up to maintain charge
neutrality. Anions, such as SO
4
2
or CO
3
2
may substitute for OH

in the structure. The formation of the


zeolitic desilication product (DSP) therefore leads to costly loss of sodium hydroxide. This reaction,
however, is necessary for lowering the level of dissolved SiO
2
to less than 0.6 g/L, the maximum
acceptable concentration.
The rate-determining step in the desilication reaction is the nucleation and crystallization of the
desilication product. Therefore, the presence of seed particles is important; without seeds, solutions
containing 0.75 g/L SiO
2
will not react in 40 min at 415 K. This has led to the paradoxical situation that
some bauxites contain too little reactive SiO
2
for good desilication. The slurry blending and storage
operation discussed earlier can be an important part of the desilication process. If the storage
temperature is above 355 K, about 80% of the reaction takes place in 8 h. More important, seed is
formed so the desilication reaction in the digest is not delayed. Very low SiO
2
concentrations can be
achieved if an excess of CaO is charged. At high temperatures, and with the lime additions, a less
soluble desilication compound (cancrinite) is formed. European plants use longer holding times during
or after digestion to facilitate desilication.
Some CaO is added to the digest even when extreme desilication is not required. The calcium reacts
with the carbonate and phosphate compounds as follows:
CaO +H
2
O Ca(OH)
2
Ca(OH)
2
+Na
2
CO
3
CaCO
3
+2 NaOH (causticization)
5 Ca(OH)
2
+3 Na
3
PO
4
Ca
5
(PO
4
)
3
OH +9 NaOH
The last reaction controls the level of phosphates in the process solution; this impurity can affect
clarification adversely. Causticization in the digest was more important when prices were such that the
sodium required by the process was supplied more cheaply as Na
2
CO
3
. Its current importance is in
control of the CO
3
2
concentration, which, at high levels, can affect precipitation. In modern practice,
the causticization reaction is carried out on dilute process solutions outside the digester. Maintaining
low concentrations and having much of the NaOH combined as NaAlO
2
are favorable to more
complete reaction of CO
3
2
with Ca
2+
.
3.1.3. Equipment
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
The equipment for digestion includes the reactor vessel, heat-exchange equipment, and pumps. The
first reactors were horizontal vessels with crude agitators mounted on axial shafts. These were filled
with a slurry of bauxite, lime, and process solution. They were closed and heated individually by
injecting high-pressure steam. At the end of the designated holding time, a discharge valve was opened
and a slurry was forced into another vessel at atmospheric pressure. Only a small portion of the steam
flashing from the slurry as the pressure was reduced could be recovered. Continuous operation was
introduced in the 1930s in which heat could be exchanged between the hot stream leaving the digester
and the cooler, incoming stream. This greatly reduces the energy requirements.
Reactors. Digester vessels, whether batch or continuous, provide intimate contact between the bauxite
and the solution for a period long enough to complete the extraction and desilication processes. The
equipment designed for this purpose is quite diverse. Agitated horizontal vessels have been replaced by
vertical units to avoid the mechanical problems with sealing the agitator shaft. Both designs have used
a series of vessels to minimize short circuiting of the flow. European practice includes use of a series of
vertical agitated vessels, each operating at a higher temperature than the preceding one. These units are
heated by flashed steam in internal steam coils. A German digester design uses concentric pipes; the
liquid being heated flows through the inner pipe while the hot slurry from the digester is returned
through the outer pipe. This tube digester has been modified by placing several tubes for the cold slurry
in parallel inside a larger outer tube. This reduces the length of the unit. The variety of digester design
is illustrated in Figures (9), (10). The flow through single-digester units may be as high as 12 m
3
/min.
The usual construction material for digesters is mild (low-carbon) steel, despite data showing that, at
the temperatures and NaOH concentrations involved, there may be stress corrosion cracking resulting
from alkali embrittlement. The presence of the [Al(OH)
4
]

ions reduces the activity of OH

in the
solution. Finely divided Fe
2
O
3
in the bauxite quickly saturates the solution with Fe
3+
, suppressing
corrosion of the metal. Some digestion equipment has been nickel plated for safety.
Flashing. In most plants the hot slurry from the digester is flashed in a series of pressure vessels until it
reaches the atmospheric boiling point. The steam generated in flashing is used in heat exchangers to
heat the flow of liquor and bauxite coming to the digester. Flashing also removes water from the
process stream, thereby accomplishing a significant portion of the evaporation needed. Normally,
heaters are tubular, but coils of tubing also are used. As few as three stages of flashing may be needed
when the digestion 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 heated. These two
modes of operation have been designated the single- and the double-stream processes. Those favoring
separate heating of the bauxite slurry, the double-stream option, feared rapid deposition of desilication
product on the heat-transfer surfaces. Experience has shown that, particularly if the bauxite slurry is
stored for blending, those fears are unfounded. The rate of fouling is no higher than for heating clean
liquor. In both options there is slow deposition of desilication product on the heat-exchanger surface
because the desilication reaction does not reach equilibrium in the digester and continues at a slow rate
wherever the solution temperature is raised. The encrustation must be removed periodically by washing
with dilute HCl or H
2
SO
4
, or by mechanical means to maintain a high heat-transfer rate.
In some plants using the double-stream system, the bauxite slurry is heated in contact heaters. These
heaters are designed much like barometric condensers. The liquid is forced to fall through the steam in
the heater in droplets or in thin films. The large surface area exposed results in high heat-transfer rates,
and because there is no metallic surface, there is no fouling. The penalty is higher dilution.
The heat needed to raise the temperature above that achieved in the flashing system can be introduced
by direct injection of steam. More often the final heating to the digest temperature is done in a separate
heat exchanger, with the energy coming from steam, hot oil, or molten salts.
Pumps. Centrifugal pumps are used in most digester systems. Those used for pumping slurries are
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built of wear-resistant alloys. A great deal of maintenance is required to keep the shaft seals operating
well. In some plants, concern about pump wear has led to the use of diaphragmpumps. In such pumps
a check valve admits the slurry to a chamber on one side of a flexible diaphragm. When that chamber is
full, oil at high pressure is forced into a chamber on the other side of the diaphragm. This moves the
slurry through another check valve into the digester. Therefore, no rapidly moving parts are in contact
with the slurry. In a J apanese modification, called the Hydrohoist, the diaphragm is replaced by a
sphere that is free to move the length of a cylinder. Slurry is kept in one end of the cylinder and the
drive fluid, which is clean process solution, is in the other end. Because of this choice of drive fluid,
leakage past the sphere is of no consequence and tight clearances are not required.
Measurement and Control. Operating variables that must be controlled are temperature, solution
concentration, and degree of desilication. The holding time is fixed by the design of the digester
vessels. As noncondensable gases are formed by the reaction of the solution with organic materials in
the digest, it is necessary to vent these gases so that the digester remains full. Venting can be controlled
by sensing the liquid level with a float or a radioactive sensor. Temperature measurement and control
are relatively simple because only the temperature from the final heater is critical. Concentration
control comes from blending the bauxite and careful proportioning of the slurry and clean solution
flows. Originally, feedforward control was used in which the composition of the incoming materials
was used to set the rates at which they were added. In modern practice feedback control is based on the
composition of the exiting solution. Chemical analyses of the solution can be used, but the time lag
involved makes this control imprecise. Nearly real-time control has been achieved by using the fact that
the conductivity of the solution at a given temperature is a linear function of the mass ratio of Al
2
O
3

and NaOH. This is the variable of interest. In modern plants the output of the sensor goes to a
computer, which in turn controls the amount of bauxite slurry pumped. Such control has reduced the
variance in concentrations to about a third of the values experienced earlier. This permits operation
closer to the maximum safe concentration with less risk of premature precipitation of Al
2
O
3
in
clarification.
3.1.4. Residue Separation
The next step in the process is the separation of bauxite residue solids from the solution. A wide variety
of equipment and procedures is used in this operation. The methods chosen depend on the quantity and
properties of the residue.
The particle size distribution of the residue solids is usually bimodal. The coarse fraction over 100 m
in diameter is termed sand, whereas the rest of the solids are finer than 10 m. The sand fraction may
range from 5 to nearly 50% of the total. The lowest amounts are in the Caribbean bauxites and the
highest are in the residue from Western Australian bauxite. In the plant the sand fraction is separated
from the process stream in liquidsolids cyclones or in more primitive settling devices. A variety of
equipment, including Dorr, Hardinge, and Aikens classifiers, have been used to wash the sand free of
process solution before it is discarded. In all of these units the sand moves countercurrently to the wash
water so that a maximum of washing is done with a minimum of water. The wash solution is added to
the balance of the process flow and proceeds to further clarification steps for removal of the fine solids.
In most plants the fine residue fraction is settled in raking thickeners of the type illustrated in Figure
(11). These vessels may exceed 49 m in diameter. Some older plants used multideck thickeners.
Difficulties in keeping the multideck units in balanced operation have led to almost exclusive use of
single-deck units in new construction.
The desanded slurry is fed at the center of the thickener and clarified solution overflows at the
perimeter. As the solution flows radially across the thickener, both the horizontal and vertical velocities
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
become very low. The solids, having a higher specific gravity than the solution, sink to the bottom of
the thickener. A settling rate of 1.5 m/h is sufficient for commercial operation. The solution
overflowing the thickener usually contains less than 0.3 g/L solids, whereas the underflow ranges from
15 to 35 wt% solids. The rotating mechanism has plows mounted at an angle to the arm. These slowly
move the settled pulp across the bottom of the thickener to a discharge port. A few units have been
designed with the discharge at the perimeter rather than at the center. The objective was to avoid the
need to elevate the units to provide access to a center discharge.
The fine solids behave as a relatively stable colloidal suspension, so they settle slowly if not treated
further. The addition of flocculants improves the clarity of the thickener overflow, the settling rate of
the solids, and the solids content of the underflow pulp. Flocculants act by binding the very fine
particles into flocs that may be several millimeters in diameter. The ratio of mass to drag forces is
increased so the flocs settle more rapidly.
Starch from grains or roots was the first flocculant; the dosage varied from 0.5 to 3 kg per tonne of
bauxite. The amount required increases as the surface of the residue increases and is affected by the
mineral composition of the residue. Starch has the advantages of being inexpensive and ubiquitous. It
does react with the NaOH in the solution to add organic compounds to the solution. In the 1950s water-
dispersible polymers were proposed as flocculants. The first compounds were effective when added at
10% of the starch charge, but they were expensive so they offered no economic advantage. More
recently, flocculants based on acrylateacrylamide copolymers have begun to replace starch. The
functional groups of these anionic flocculants can be modified to suit specific operating conditions.
Different materials may be used in the thickeners and in the washing operation. In some cases a small
amount of starch is added to the synthetic flocculant to improve overflow clarity. These synthetic
materials now offer an economic advantage because they have been made less expensive and more
effective.
With the residue concentrated in the thickener underflow, the next task is to wash it free of process
solution so that it can be discarded. This is usually done in countercurrent decantation systems using
washing thickeners that are similar in design to those used for settling. The washing operation is done
in as many as seven stages with the solids moving countercurrent to the wash stream. This is illustrated
in Figure (12). An equation can be written for each stage expressing a material balance between soluble
materials and dilution. Computer models of the washing system allow accurate prediction of
performance.
In residue washing, the objective is to minimize both the value of the soluble salts lost and the cost of
evaporating the added wash water. The solubles in the discarded pulp can be reduced by increasing the
solids content of the underflow. This reduces the amount of solubles carried from one stage to the next
so that dilution is more effective and can be accomplished by using more flocculant or by increasing
the holding time in the thickener. There is some risk in the latter change. If some undissolved gibbsite
or boehmite remains in the residue, it may induce precipitation with a resulting loss of Al
2
O
3
.
In some plants vacuum drum-type washing filters are used to replace some or all of the washing
thickener stages. The solids content of the residue may be increased to 5060 wt% by filtration.
Therefore, only about 33% as much solution is needed compared to plants using thickeners and this
results in a great increase in the effectiveness of washing. Calculations for countercurrent washing
show that two stages discharging at 55% solids are more effective than six stages operating at 20%
solids.
Another approach only recently introduced into plant practice is called the deep thickener. This
equipment was developed in the British coal industry to concentrate the slimes from coal washing. In
the deep thickener, increased quantities of flocculant are used, and a column of residue pulp up to 10 m
deep is maintained. The hydraulic pressure of the deep column appears to densify the pulp so that
underflow solids approaching the concentration of filter cake are obtained. The overflow from these
units contains more solids than the flow from standard thickeners, but the units are finding use in
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concentrating residue for washing and for disposal. The simplicity of the equipment adds to its appeal.
The final stage of clarification is polish filtration of the solution, sometimes called clear pressing. Most
of the residue solids have been removed from the process solution in the previous steps, but product
purity must be protected by removing the few particles of solids remaining. Filter presses are used most
widely.
Another approach to polish filtration is use of a stationary filter in which the medium is uniform, fine
sand a meter deep. Gravity provides the force to move the solution through the sand bed. During
operation, the fine solids are mixed with the sand, from which they are elutriated at the end of the
cycle. Such filters can be automated and are especially effective with residues that are difficult to
process.
Close attention is required to keep the solids content of the filtrate down to 0.5 mg/L to protect product
purity. Light transmission of the filtrate is used as an index of clarity. Purity originally was determined
visually, but nephelometers are used now. If evidence of solids is found, the filtrate from each filter is
scanned to locate the source. Some solids may pass through the filter cloth before a layer of solids
forms to serve as a barrier, so it is common practice to recycle the first portion of filtrate.
Control in clarification has two major objectives; the solids must be removed and the washed residue
must be prepared for discard, using a minimum of wash water. The first objective is achieved by
measuring the cloudiness of the filtrate. High solids in the underflow are dependent in part on the
retention time in the thickener, so measurements must be made of the pulp level in the unit. Automatic
determination of the interface between clarified liquid and pulp has been 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 excessive. 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 335345 K before
precipitation. This cooling is usually done in a flashing system analogous to that used in recovering
heat in digestion. Because the temperatures are below the atmospheric boiling point, the flash vessels
and the heat exchangers must operate under vacuum. Most of the heat removed by flashing is
transferred to the colder solution returning from precipitation. Plate-type liquidliquid heat exchangers
have also been used. A recent development is to cool the solution further midway through the
precipitation operation. This allows higher recovery of Al
2
O
3
without using conditions that lead to
excessive nucleation of product.
Recovery of the Al(OH)
3
from the process solution is known as precipitation, decomposition, or
Ausrhrung. The reaction is the reverse of the digester reaction given earlier. The cooling done after
digestion and filtration has moved the solution into an area of the solubility diagram known as the
metastable region. The concentration and temperature are such that the solution is supersaturated with
Al(OH)
3
but is not saturated enough for spontaneous crystallization. This is illustrated by Figure (13).
At the digest temperature, T
1
, the Al
2
O
3
concentration is increased to point P on the diagram. Cooling
to temperature T
2
results in crossing the solubility curve into the metastable region. Addition of
Al(OH)
3
seed at this point causes precipitation and the concentration of Al
2
O
3
approaches the solubility
curve at T
2
. The additional cooling recently adopted moves the solution conditions further to the left in
the diagram above a lower point on the solubility curve.
The kinetics of the precipitation reaction are represented by the equation:
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
where:
c =Al
2
O
3
concentration, g/L
k =constant
E =activation energy, about 59000 J /mol
R =8.31441 J mol
1
K
1
T =temperature, K
A =seed area, m
2
/L
c

=concentration at equilibrium

The reaction is second order, i.e., the rate is affected by the square of the difference between the actual
Al
2
O
3
concentration and the equilibrium concentration. The operating temperature affects the
equilibrium concentration and the reaction rate. Because seed area is important, the seed charge must
be as high as can be maintained while meeting other operating objectives.
The first objective in precipitation is to produce Al(OH)
3
that, when calcined, meets the specifications
for metallurgical alumina. These specifications are discussed in Section 5.2. Typical Specifications for
Metallurgical Alumina. The second objective is to obtain a high yield from each volume of solution.
This increases the plant capacity and reduces the amount of energy spent in heating and pumping the
solution. At the same time, the processes serving to create new Al(OH)
3
particles must be controlled so
that the number of seed particles created equals the number of particles leaving the system as product.
This requires balancing nucleation, agglomeration, growth, and particle breakage, so a combination of
science and art has developed.
About 2 10
10
nuclei must be formed in each liter of solution to balance the process. The rate of
nucleation is a strong function of both the degree of supersaturation and of temperature. Very few
nuclei are formed if the temperature is above 350 K. A change in the operating temperature of only 5 K
will change a system from a net producer to a net consumer of nuclei. Temperature changes of 23 K
are the most frequently used control measures.
The nuclei grow by accumulation of Al(OH)
3
on their surface if they become large enough to be viable
seeds. The rate of growth can be as high as 9 m/h, but it is generally much lower. The growth rate is
independent of the particle diameter. Particles also increase in size by agglomeration. By a process that
is not well understood, the nuclei form clusters in the first few hours of the cycle in batch precipitation.
When the supersaturation is low, this agglomeration does not occur. Some speculate that when the rate
of precipitation is high, the Al(OH)
3
is not well crystallized when it is first deposited on the seed. This
later may serve as the bond for agglomeration. At low supersaturation the deposited material is better
ordered. The action of mechanical equipment in precipitation can break fragments off crystals or break
up agglomerates, creating secondary nuclei, but this is not a major factor in most plants.
Figure (14) is an electron micrograph of some Al(OH)
3
produced in a plant operation. The particles are
obviously the result of agglomeration. Those agglomerates having fewer particles can be shown by thin
-section micrographs to have grown radially from an agglomerate of relatively few nuclei.
In Figure (15), the Al
2
O
3
concentrations in experimental precipitations is shown as a function of time
and temperature. The slopes of these curves indicate the rates at which precipitation is progressing. All
curves show a high rate at the start and appear to be approaching a final value asymptotically. The final
concentrations were well above the saturation level, but in these as in plant operation the rate became
unusually low, so the process was terminated.
Precipitators are vertical cylinders; the height, which may be 30 m, is usually 2.53.0 times the
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
diameter. The seeded slurry is circulated to maintain intimate contact between solids and solution.
Early precipitators circulated the material by means of a central air lift pipe. Air introduced at the
bottom of the pipe reduced the apparent density of the slurry within the pipe. This caused slurry to flow
into the bottom of the pipe to establish circulation. Modern precipitators are circulated mechanically by
impellers up to 3 m in diameter operating in a draft tube. In these units the flow is downward through
the tube, so the tank bottoms are nearly flat to reverse the flow and cause upward motion of the slurry.
Tanks with air lifts have conical bottoms to direct the flow to the central air lift.
Originally, precipitators were filled individually 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 operation 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 solution moves by gravity through channels connecting 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 operating problems. One is to
avoid passage of the slurry across the tank tops, thereby reducing the retention time. Movement of
solids from tank to tank is also a problem. An ideal system would retain fine particles in the tanks and
move only the coarse material to the discharge. This is not possible, so a compromise method of
operation must be found. Precipitation takes place at constant conditions in each tank instead of
following a continuous curve, as in Figure (16). This tends to decrease production per tank, but the loss
is more than recovered because the tanks are always in use.
Several patterns have been used to supply the seed for precipitation. The earliest was to neutralize a
portion of the solution. An Al(OH)
3
gel was precipitated that changed into fine crystallites on aging.
This very fine material was grown through at least one cycle to provide an active seed for product
precipitation. The more common approach is to use fine particles, produced in the operation, as seed.
The slurry leaving precipitation is classified into a coarse product fraction and one or more fine
fractions. The fines are returned to the process to grow to product size. Classification is done by
controlling the flow rate through tanks so that the fines are elutriated. Liquidsolid cyclones are
coming into use because they provide more accurate separations. The seeding and classification
systems have become increasingly complex. In modern plants at least three fractions are separated. In
some plants the agglomerates formed from fine seed must pass through the system once more before
becoming product. This reflects the belief that the agglomerates must be made tougher by deposition of
additional Al(OH)
3
so that they do not disintegrate in calcination and subsequent handling.
In a modification [47], a relatively small charge of fine seed is added to the first tank in a series. This
promotes agglomeration. Then, additional coarser seed is added to the second or third tank to provide
the large seed area needed for high production. As indicated previously, cooling may be done between
units in a series to increase the supersaturation in the final tanks, thereby increasing the production rate.
A further change in modern plants is to filter the seed slurry being recycled. This decreases the amount
of spent solution returning to the system and increases both the Al
2
O
3
concentration in the first tank of
the series and the overall production.
The control variables available to the precipitation operator are the temperatures in the system; the flow
per unit, which translates into holding time; the amount of seed; and the particle size of the seed. Some
of these variables are difficult to control, so the system usually cycles slowly from coarser than desired
to finer. There is enough inventory in the process so that minor cycles can be tolerated without
affecting plant output.
3.1.6. I mpurities
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
The impurities in the product Al
2
O
3
are affected by all of the foregoing operations, including selection
of the bauxite. There are at least three classes of impurities. The first is residue solids that are not
removed in clarification. The large surface area of Al(OH)
3
in precipitation effectively sweeps up these
solids into the product. The preventive measure is increased vigilance in filter maintenance and
operating. The second class is materials that are in true solution, such as sodium and gallium. The third
group includes materials that are in solute form at the temperature of digestion but precipitate later in
the process. Their solubilities may be only milligrams per liter and return of the solution to equilibrium
at lower temperature may be slow. If precipitation is not completed before filtration, the remaining
impurities appear in the product. There are also other impurities that do not fall neatly into these
categories.
Sodiumis the main component of the process solution and is also the largest contaminant of the
product. The Na
2
O content of alumina can be decreased by increasing the seed charge and by
increasing the precipitation temperatures. The real variable that these operating changes help control is
the rate of crystal growth. Higher temperatures, greater seed area, and lower Al
2
O
3
concentrations all
slow growth and give impurities more time to diffuse from the surface. By proper control of these
variables an order of magnitude decrease in the Na
2
O content of a commercial product has been
achieved. Some sodium is lost in the HallHroult cells during smelting by absorption into the cell
lining and by conversion to sodium metal, so complete absence of sodium in metallurgical alumina is
not necessary. The target is to balance the input to the cells with the losses. This requires Al
2
O
2

containing about 0.40.5 wt% Na
2
O.
Galliumis a ubiquitous component of aluminous ores. Its chemistry is similar to that of aluminum, so it
accumulates in Bayer process solutions until an equilibrium is reached at about 0.2 g/L. The gallium
content of Al
2
O
3
is a linear function of the gallium concentration in the solution. Therefore, the amount
leaving in the product equals the input. Because gallium is in true solution, the same changes that lower
the Na
2
O content of the product lower the gallium content. Only in the production of high-purity metal
has there been concern about the gallium content of alumina. About 10 t/a of gallium is recovered from
Bayer process solutions. This is the best source for the production of gallium ( Gallium and Gallium
Compounds).
Silicon is a component of many aluminum alloys, yet the specification for Al
2
O
3
is less than 0.02%
SiO
2
. This value is only 25% of that specified 50 years ago. The SiO
2
is in solution, but it appears to
be added to the product through a slow continuation of the desilication reaction (Section 3.1.2.
Digestion). There is also evidence that if the rate of Al
2
O
3
deposition on seed is not high, the seed
surface becomes at least partially covered with desilication product, thereby becoming less active as a
seed for Al(OH)
3
precipitation and more active toward SiO
2
. This impurity is controlled by driving the
desilication reaction nearer to completion. Lowering the SiO
2
concentration of the solution below 0.1
g/L gives a product containing less than 0.003% SiO
2
.
Potassiumis undesirable in the Al
2
O
3
because it may destroy the graphite in HallHroult cells by
intercalation, i.e., it diffuses between the layers of the graphite structure, thus expanding its volume.
Although it is soluble in Bayer solutions, there has not been a recorded instance of K
2
O concentrations
becoming high enough to affect the Al
2
O
3
quality.
Iron(III)oxide (Fe
2
O
3
) as an impurity in Al
2
O
3
has been the subject of much investigation. It is soluble
up to ~0.1 g/L in the solutions at digest temperatures (400500 K), but only to ~0.001 g/L at 333 K
[48]. This reconciles the observations that Fe
2
O
3
behaved at times as if it were in solution and as a
colloid at others. There are several iron minerals that can serve as sources for the impurity. Hematite (o
-Fe
2
O
3
) and goethite (o-FeO(OH)) are present in most bauxites. Goethite is slowly converted to
hematite in high-temperature digests, particularly if CaO is present. This conversion improves
clarification because hematite settles better than goethite. The mineral siderite (FeCO
3
) present in some
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
bauxites not only is a source of iron but also reacts with NaOH to increase the amount of causticization
needed. Pyrite (FeS
2
) is almost insoluble in Bayer solutions; its adverse effects occur when the sulfur is
oxidized to sulfate in the presence of air and water. The sulfate will react with NaOH to form Na
2
SO
4

which has to be removed periodically.
Paradoxically, there is less difficulty with Fe
2
O
3
as an impurity in processing bauxites containing a
large amount of iron oxides. This is probably because the iron oxides serve as seed and hasten
hydrolysis of the NaFeO
2
formed in the digest. Running the solution over iron oxide particles before
filtration has been effective in controlling this impurity. Another process for lowering the iron content
of Al
2
O
3
is termed step precipitation. The filtered Bayer solution is lightly seeded with Al(OH)
3
for a
short time to precipitate up to 3 g/L Al
2
O
3
. The seed and the small amount of precipitation effectively
sweep the colloidal iron hydroxide particles from the solution, leaving an Fe
2
O
3
concentration of less
than 0.005 g/L.
Calciumalso is a common impurity. The presence of increasing amounts of Na
2
CO
3
in the Bayer
solution seems to increase the CaO in the product. The calcium content of alumina, as with sodium,
needs to be controlled such that the HallHroult cell bath can come to an equilibrium level acceptable
for cell performance. Calcium can be controlled by step precipitation or by lowering the carbonate
content of the solution.
Lithiumis also acceptable in HallHroult cells. It can be removed by step precipitation.
Other metallic impurities that appear in many bauxites in small amounts are chromium, copper,
manganese, titanium, vanadium, and zinc. Generally, these impurities are not so concentrated that
removal processes are required. Sulfide salts have been added to precipitate copper and zinc. The
chromium is a problem only if it is oxidized; the organic salts in the solution are usually a sufficient
reductant. The addition of manganese compounds as oxidants for organic material has been reported.
Anions, such as carbonate, chloride, fluoride, and sulfate, are known to interfere with Al(OH)
3

precipitation. The carbonate ion is controlled by addition of lime, although processes have been
reported in which Na
2
CO
3
is removed by evaporative crystallization or by cooling the solution to 260
K. The sulfate and chloride ions usually are controlled naturally, as their salts are incorporated in the
desilication product in sufficient quantities to maintain an equilibrium. There are commercial
operations in which the sulfate salt is removed by evaporation and crystallization. The least soluble salt
is schairerite (Na
2
SO
4
NaF), and when the fluoride ion is depleted, burkeite (2Na
2
SO
4
Na
2
CO
3
)
appears. The fluoride ion is almost never present in quantities large enough to be harmful.
Many bauxites contain phosphate minerals. Apatite (3Ca
2
P
2
O
8
CaF
2
) does not react in the process;
indeed, this compound or its hydroxy counterpart is formed when soluble phosphates react with
calcium in the digest. Aluminum phosphates, such as wavellite (4AlPO
4
Al(OH)
3
9H
2
O) do react,
forming Na
3
PO
4
as the soluble phosphate. The phosphate ion interferes with flocculation of bauxite
residues containing goethite, probably by competing for attachment sites [49]. The concentration of
phosphates never is high enough to interfere with Al
2
O
3
purity. Addition of CaO to the digest is the
control measure.
Organic matter in bauxite, whether it be roots and twigs from plants or humic acids from decayed
matter, reacts in the digest to form a wide variety of organic compounds. Some operation process
streams have exceeded 15 g/L organic carbon in solution. There is evidence that larger molecules are
oxidized in the process all the way to Na
2
CO
3
and sodium oxalate (Na
2
C
2
O
4
). In addition some, but not
all, of the organic compounds may interfere with precipitation [4].
The effect of sodium oxalate on processing has not been quantitatively determined, yet many plants
incorporate equipment for crystallization of the oxalate salt from the solution. Others wash this salt
from the Al(OH)
3
seed and recover it from the wash water. The evidence is overwhelming that
operations are improved by the oxalate removal techniques. Early removal processes included
evaporation to high concentrations followed by centrifugal separation of the gelatinous salt mass. In
other plants, a portion of the solution was mixed with bauxite or Al(OH)
3
and heated to 1280 K. This
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
destroyed the organic compounds and formed NaAlO
2
, which could be recovered in the process. A
German process adds magnesium salts to the digest to remove the deleterious organic compounds. Still
others are investigating methods of oxidizing the organic material in the solution [50].
3.1.7. Calcination
The final operation in production of alumina is calcination. The temperature of the Al(OH)
3
is raised
above 1380 K resulting in the reaction:
2 Al(OH)
3
Al
2
O
3
+3 H
2
O
As discussed in Section 2.2. Composition and Properties, this reaction can take several pathways and
several transition forms may appear. The end of all pathways is o-alumina. In older European practice,
a major portion of the alumina was converted to the o-phase, sometimes by the addition of a fluoride
salt to lower the temperature of transformation. In American practice, calcination always has been less
severe; so, normally, 20% of the alumina is in the o-phase.
Before calcination, it is necessary to wash the process solution from the coarse Al(OH)
3
. This is done
countercurrently, using storage tanks and filters. As in residue washing, increasing the number of
washing stages and the concentration of solids leaving each stage improves the effectiveness of
washing. Vacuum filters of several designs have been used for the final separation. The early Oliver
and Dorr drum filters have been replaced by horizontal rotary filters because better washing can be
achieved. The quality of the wash water is of some concern because such impurities as calcium and
magnesium can be adsorbed on the surface of the Al(OH)
3
.
Earlier, calcination was done in reverberatory furnaces. These had neither the capacity nor the thermal
efficiency required, so they were soon replaced by rotary kilns. These kilns are cylinders that may be
3.5 m in diameter and over 80 m long. They are mounted on bearings and rotate about an axis inclined
at a small angle to the horizontal. Damp Al(OH)
3
from the filters enters the upper end and slowly
tumbles toward the lower end, traveling against a stream of hot gas formed by combustion of natural
gas or oil at the discharge end. Early kilns were less than 40 m long, but longer units have better
thermal efficiency and higher capacity.
Product coolers were added to kilns so that part of the heat in the incandescent product could be
transferred to the combustion air. Early coolers followed designs developed in the cement industry and
were themselves rotary units much like, although smaller than, the kilns. Improved coolers fluidize the
product Al
2
O
3
around heat-exchange surfaces, often in several stages. In such coolers, the heat can be
recovered in combustion air or in wash water and the product can be cooled readily to 425 K.
The progressive adoption of large-capacity stationary calciners has reduced fuel consumption for
alumina calcination to ca. 3.1 GJ per tonne of alumina, which compares to ca. 4.5 GJ per tonne for
earlier rotary kilns. Several stationary calciner designs with capacities of >2500 t/d alumina are now
commercially available. In stationary calciners, a combination of fluid beds and stages in which the
solids are transported in suspension is used. Figure (17) is a schematic diagram of a commercial unit
capable of calcining 1500 t/d.
The Al(OH)
3
is washed and dewatered on the filter (a) and is conveyed into the flash dryer (b), where it
encounters hot gas from cyclone (g). The gas evaporates the free water from the particle surfaces.
Because the temperature exceeds 480 K, a portion of the water of hydration also is driven from the
crystals. Cyclone (c) separates the solids from the gas. The gas, cooled almost to its dew point, leaves
the unit through the electrostatic precipitator (j), where dust is recovered. Vessel (d) serves as a surge
buffer to smooth the flow of solids through the unit. The solids are separated in cyclone (g) to enter the
vessel (f) where combustion of fuel is taking place. Vessel (e) allows a holding time at the calcination
temperature so that the water content of the product is low. A small amount of fuel can be burned in
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this vessel if a higher temperature is desired. In this design the flow of solids is counter to the flow of
the gas.
The solids are cooled, also in counterflow, by the combustion air in unit (h). Final cooling is in a
fluidized bed unit (i). In the fluidized unit a small amount of air is introduced through a membrane at
the bottom. This lifts but does not entrain the solids, so they behave much like a fluid. Heat is
transferred at a high rate to air or water flowing through tubes submerged in the bed. The product
Al
2
O
3
can be cooled below 400 K with all of the recovered energy being used in the process.
The great advantage of the stationary units is that the heat required for calcination is 3100 MJ /t. The
capital costs are lower than for rotary kilns of equal capacity, and the maintenance costs are lower
primarily because the refractories are not subjected to rotational stresses. Because the capacity per unit
is high and automation is quite easy, the labor requirements are low. The stationary units are being
installed in retrofitting older plants as well as in new construction.
Alumina calcined in stationary kilns has a lower o-alumina content and a higher surface area than
alumina calcined at the same temperature in a rotary kiln. This reflects the shorter residence time and
the absence of a high-temperature flame in the static units. Photomicrographs show that the rapid
temperature rise creates vapor pressure within the particles that tends to fracture large crystals.
The characteristics of the metallurgical alumina are controlled mostly by the time and temperature of
calcination. The important parameter is the reaction between the Al(OH)
3
feed and the flow of fuel.
The fuel must be free of impurities that can contaminate the alumina. Sulfur and vanadium in fuel oil
are limited by concern for product purity. The amount of combustion air must be sufficient to burn the
fuel completely without the use of a great excess that increases the gas flow and thereby reduces the
thermal efficiency. Factors affecting fuel economy and alumina quality in modern stationary calciners
are reviewed in [51].
3.1.8. Evaporation
As is shown on the flow sheet for the Bayer process (Fig. (7)), the solution continuously cycles through
the plant. Consequently, any wash water used must be evaporated so that the solution volume can be
controlled. About 10% of the flow is evaporated in the two cooling areas by being flashed into steam.
In high-temperature digesters, the amount of flash evaporation is even larger. At least one plant
processing high-grade bauxite was designed without any additional evaporation capacity. In most
cases, the economics require installation and operation of evaporators. The objective is to minimize the
summed costs of evaporation and the value of the soluble salts lost by incomplete washing. The
minimum is usually attained with a net dilution of the residue of 1.52.0 kg/kg.
Table (7) lists the input and exit streams that compromise the dilution balance in an operating plant.
Efficiency demands that all of these flows be monitored.
Several evaporator designs are used in Bayer plants, but nearly all designs are used in multiple-effect
configurations. In such units each stage operates at a lower pressure than the preceding one. Therefore,
the vapor evaporated from the solution in the first stage is at a temperature high enough to heat the
solution in the second stage, causing it to boil. This continues to the final stage, where the vapor is
condensed. The condenser operates under vacuum so a jet pump is necessary to remove
noncondensable gases from it. The more times the latent heat is used, i.e., the more stages that are
present, the more water can be evaporated by the fuel steam used in the first effect. With Bayer
solutions the maximum number of effects is six. This is because the boiling point of the solution is
elevated 58 K by the dissolved solids. This reduces the steam temperature in each effect; with many
effects there is little temperature difference available to cause evaporation.
An unconventional design called continuous regenerative evaporators has been used in some plants.
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These units are similar to the heating and flashing equipment used in digestion in that the feed is heated
through up to ten stages without evaporation; the hot solution is then flashed through an equal number
of stages and the steam is used for heating the feed. These units are not as efficient as most multiple-
effect evaporators. The design choice is based on economics. Special evaporator designs may be used
when it is necessary to crystallize organic or inorganic salts from the solution. In such designs pumps
are used to increase the thermally induced flow through the tubes in the heaters. The heat-transfer
surfaces in evaporators must be cleaned periodically to remove encrustations of desilication product
and soluble salts.
Evaporators are controlled primarily by changing the amount of steam used. The flow of feed solution
is regulated so that crystallization of soluble salts is either induced or avoided, depending on the
operating mode. Temperature readings at each effect are compared to design values to indicate
operating difficulties.
3.1.9. Residue Disposal
The most important environmental problem in the Bayer process is disposal of the bauxite residue. The
solution left with the residue after an economical amount of washing is still very alkaline and cannot be
allowed to contaminate ground water. Furthermore, the desilication product in the residue which is in
contact with water has the capacity to exchange sodium for hydrogen. An aqueous slurry of the residue
that had been washed with 1000 times its mass of distilled water still reached a pH value of 10.5 on
standing. The undrained fine residue, even after years of consolidation, does not have enough strength
to support buildings or equipment. These properties make disposal a difficult problem.
Previously, disposal was to a marine environment where the alkalinity was diluted by large quantities
of water. This method has been used in the seas off Europe and J apan and in a river in the United
States. Studies by environmentalists have indicated little damage to flora or fauna by the residue in a
disposal area [52]. Today, however, environmental concern is so great that any new refinery is unlikely
to be permitted to use marine disposal.
Early inland refineries simply dammed a convenient valley or built retaining dikes on flat land to form
residue disposal areas. In some cases, the sandy portion of the residue was used to build the dikes. This
method can be effective and cheap if care is taken to protect the surroundings by proper sealing
techniques. The compacted residue has a lower permeability than many clays; yet, there have been
isolated leaks into aquifers from such impoundments. Improved designs have been developed.
In Germany, retaining dikes are built with a portion of the structure designed to be porous. The dilute
solution draining from the residue is channeled by the porous sections into water-treatment facilities
before being discarded. In some cases, the dike material exchanged ions with the solution so that little
treatment was needed. The draining allowed consolidation of the residue so that it could support
equipment. An American firm used a drained lake in which the bottom of the disposal area was covered
with sand in which draining pipes were laid. The residue was pumped to these areas in the traditional
manner as a dilute slurry. Most of the conveying water was decanted, while some percolated through
the deposit to the drains. This design has two advantages: the residue consolidates better, so the storage
capacity of an area is increased, and the hydraulic head on the bottom is reduced to zero, so that
leakage is unlikely. Recent lakes have been built using the sand drains on top of seals of clay and
plastic film for additional environmental safety.
Another modern disposal method, called dry stacking, takes advantage of the thixotropic nature of the
residue. By some method, usually vacuum filtration, the residue is concentrated to 3550 wt% solids.
The slurry is agitated to reduce its viscosity by as much as two orders of magnitude and pumped to a
disposal area. There it flows in lava-like fashion over the surface, establishing a slope away from the
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discharge point. In the absence of shear, the viscosity of the slurry increases and flow stops. Water does
not separate from the slurry and the slope causes rain to run off rapidly, so the surface usually is losing
water to the atmosphere. The surface becomes deeply fissured, further assisting drying. In about 90
days the residue may dry to 75 wt% solids, far drier than in any of the other disposal methods. In this
state, it can support heavy earth-moving equipment and can be recovered or used for increasing the
height of retaining dikes. This method maximizes the storage capacity of a given area and seems to
pose the minimum threat to the environment. It does require construction of a permanent lake area for
water storage and for cooling water. If any use is to be made of the residue, recovery is relatively easy.
Many investigations have been directed toward finding a commercial use for bauxite residue. The high
iron content of some residues suggested production of pig iron. The quality of the iron was poor and
the amount of slag formed exceeded the original amount of residue. Similarly, chemical processes have
been developed for recovery of Al
2
O
3
, Na
2
O, and TiO
2
from residue. Although all are technically
possible, none has been feasible economically. Small quantities of residue have been used in making
Portland cement, and smaller quantities have been used as a mold wash, as an insulating material, and,
after reaction with H
2
SO
4
, as a water treatment. No chemical use is likely to consume a significant part
of the residue [1], [5].
The residue is claylike and can be used in ceramic materials. The sodium causes formation of glasses at
1450 K, giving a vitreous bond. Bricks have been made commercially, but economic factors and other
shortcomings of the brick have eliminated this use. Sintering the residue into aggregate for concrete
may be economical where natural aggregate is not available.
In Texas, agronomists have shown that the residue can be used to neutralize acidic soil, replacing
limestone. The cost of preparing the material for application and the logistics argue against extensive
use. The conclusion is that large-scale use of bauxite residue is unlikely, so efforts should be directed
toward reclamation of disposal areas.
3.1.10. Energy in the Process
Approximately 16 MJ are required to produce a kilogram of Al
2
O
3
. The worldwide range is 7.432.6
MJ /kg [48]. Variations in the quality of bauxite, plant design, and the size of the plants are the reasons
for the large differences. Even with existing plants, large improvements in energy usage can be made.
The Aluminum Association (USA) reports that the energy used per unit of alumina production in 1980
was 68% of the energy used in 1972 [54]. The energy used in mining is less than 5% of the total and is
difficult to change. The energy for transporting bauxite is double that for mining it, because the average
tonne of bauxite used in the United States is transported 4700 km. The situation worldwide is different
because much of the bauxite is refined close to the mines.
Within the refinery, more than half of the energy is used for pumping and heating the solution and for
evaporation. The previous discussion (Section 3.1.3. Equipment) has shown that plant design can affect
heat recovery and minimize energy use. Emphasis is being placed on increasing the amount of Al
2
O
3

recovered from less than 50 g/L to over 65 g/L; some claim yields as high as 100 g/L. Because energy
is more closely related to the flow of solution than to yield, the energy savings are large. The static
calciners are nearly as efficient as they can be made because the temperatures of the gas and of the
product leaving the units are very low. The change from rotary kilns has made up a large portion of the
savings. There are still opportunities to improve operating practice and design to reduce energy
consumption [55].
Continued ...
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3.2. Economic Aspects
The largest cost elements in alumina production are raw materials, energy, and capital-related costs for
the production equipment. Labor, operating supplies, and miscellaneous costs are much smaller than
these three.
Bauxite is the most important raw material. Its cost includes those for mining, transport, levies, and
taxes. In addition, the relative quality of the bauxite ore influences the expenditures for necessary
reagents. Mining is relatively inexpensive because most deposits are covered with only a shallow
overburden and can be mined with efficient equipment. Since the formation of the International
Bauxite Association (IBA), levies and taxes have become a large part of the cost of bauxite. These
costs have become relatively stable because most are related to the selling price of aluminum. The
availability of bauxite from outside the IBA countries has allowed the effect of supply and demand to
influence this cost. Where levies are not imposed, some system of taxation provides income to the
producing 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 by truck or conveyor belt to the refinery. Other bauxite
may travel more than halfway around the world. The characteristics of bauxite most important in
influencing its value are the available alumina and the reactive silica contents. The latter quantity has a
great effect on the amount of sodium hydroxide and lime required in processing. Bonuses are given for
high available alumina values, and penalties are charged for excessive silica.
In Section 3.1.10. Energy in the Process, values were given showing the fourfold range in energy used
to produce alumina. The most important variables are the plant design and the quality of the bauxite
being processed. The most energy-efficient bauxites are gibbsitic, with very low residue content.
The capital costs also show wide variation. In 1990 U.S. dollars new installations may cost from $700
to $900 per annual tonne of capacity. The variables are design factors, location, capacity, and the
properties of the bauxite to be processed. Much of the world capacity was constructed before
construction costs were inflated and so has lower capital costs. The effect of capacity is also large, and
plants producing 2 10
6
t/a have costs well below those of plants producing less than 10
5
t/a.
Alumina is traded on the world market as a commodity. Not all smelters have alumina capacity
dedicated to them; they buy alumina on contract. Long-term contracts are common. In other instances,
alumina is bought when needed at spot market prices. Since 1980, alumina has sold on the spot market
for less than $150 to over $280 per tonne, reflecting a change in the relationship between supply and
demand. Economics do not always control production because many corporations own refineries to
supply their smelters. In other instances, national governments own a significant portion of a refinery
and for political reasons may choose to operate in a noncompetitive situation. Costs per tonne of
alumina can, under unfavorable conditions, exceed $200, although efficient plants may produce at
roughly half this figure.
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4. Other Processes for Alumina Production
4.1. Raw Materials
Many investigations have sought processes to replace the Bayer process by using raw materials other
than bauxite [2]. Clay, primarily kaolinite, has been most considered because it can contain up to 39%
Al
2
O
3
( Clays). Other materials, including anorthosite, nepheline, coal wastes, and fly ash, have been
candidate raw materials. Yet, less than 2% of the world supply of alumina is not made by the Bayer
process. This happens only where use of a domestic raw material and production of a desirable
byproduct change the economic picture. Alumina from ores other than bauxite normally costs 1.52.5
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.
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4.2. Alkaline Processes
Sodiumcompounds, such as Na
2
CO
3
, react at 1280 K with the Al
2
O
3
in aluminous ores to produce
water-soluble NaAlO
2
. This compound can be leached from the sinter with water and the solution
treated to remove impurities; the purified solution is neutralized with CO
2
to recover Al(OH)
3
. The last
step regenerates the Na
2
CO
3
for recycle. Difficulty arises because the aluminous ores contain SiO
2
,
which also reacts in the sinter to form soluble Na
2
SiO
3
. In processing, the desilication reaction
discussed in Section 3.1.2. Digestion takes place, so the net recovery of Al
2
O
3
is small or zero. If 2 mol
of CaO, usually as limestone, is charged for every mole of SiO
2
in the raw material, insoluble calcium
silicate compounds are formed. Under proper leaching conditions the NaAlO
2
can be recovered from
such sinters with only slight loss.
The process has been used commercially in two American plants to recover most of the Na
2
O and
Al
2
O
3
lost in the desilication product formed while treating high-silica native bauxite. A schematic
flow sheet is given in Figure (18). The same process was investigated by the U.S. Bureau of Mines in a
large pilot plant using anorthosite as the raw feed [51]. [Anorthosite is a mixture of the minerals
anorthite (CaAl
2
SiO
8
) and albite (NaAlSi
3
O
8
).] Unless the composition, sintering, and leaching were
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closely controlled, the residue formed a gel in leaching and became very difficult to filter.
In a variation of the sintering approach, calciumreplaces the sodium so that calcium aluminate (3CaO
Al
2
O
3
) is formed as well as calcium silicate (CaSiO
3
). The calcium aluminate reacts with Na
2
CO
3
in an
aqueous leach to form NaAlO
2
.
3 CaO Al
2
O
3
+3 Na
2
CO
3
+2 H
2
O 2 NaAlO
2
+4 NaOH +3 CaCO
3
In carbonation, Al(OH)
3
is formed and the Na
2
CO
3
solution is regenerated. Nepheline, (Na,K)AlSiO
4
,
is treated by this process in the former Soviet Union. The calcium silicate residue is processed to make
about 10 t of cement per tonne of alumina. The two products make the process viable here.
In the Pedersen process, sintering was replaced with a reducing fusion so that ferric ions in the ore were
reduced to metal. Iron and the calcium slag were separated by decantation. During cooling, the CaSiO
3

passes through a crystalline phase change and the resulting stresses reduce the slag to powder [1], [2].
The sinter processes suffer economically for several reasons. The energy for sintering and for
evaporation of the leach solution must be added to the energy required from operations analogous to
those in Bayer processing. The capital investment is increased by the need for sintering equipment, and
although limestone is inexpensive, the quantity required is so large that the expense is considerable.
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4.3. Acid Processes
All of the acid processes follow the general flow sheet given in Figure (19). Usually the clay is
prepared by grinding and roasting to about 1000 K. The roasting changes the kaolinite to meta-kaolin,
from which the aluminum can be dissolved as the acid salt. The roasted clay is leached in an acid
solution, usually at the atmospheric boiling point. Some investigators have chosen to leach at elevated
temperature for processing advantages even though corrosion problems become more severe [1]. The
siliceous residue is separated using sedimentation and filtration as in the Bayer process. Small amounts
of iron salts remain in the clarified solution. These salts are removed by extraction with an organic
compound that forms a complex with the iron but not with the aluminum salts. The organic solution is
decanted from the aqueous phase and is treated to separate the iron salt and to regenerate the organic
extractant.
A hydrated aluminum salt is recovered from the aqueous solution, usually by evaporation and cooling
to cause crystallization. In the hydrogen chloride process, advantage is taken of the low solubility of
AlCl
3
in HCl. The HCl gas is absorbed in the solution both to regenerate the acid for leaching and to
precipitate AlCl
3
6H
2
O. In all acid processes the hydrated salt is decomposed to Al
2
O
3
by heating to
1300 K. Both water and the acid radical are driven off, and the acid is absorbed for recycling.
The U.S. Bureau of Mines sponsored a cooperative effort with several aluminum companies to
investigate acid processes for recovery of alumina from clay [56]. For several reasons the HCl process
was preferred: the reagent is inexpensive, processing conditions are not severe, and the salt can be
recovered without evaporation. The HCl is not decomposed in calcination, and the water content of the
acid salt is half that of other acid salts. Despite these features the process is not competitive
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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
corrosive solutions. A process disadvantage is that the Al
2
O
3
is physically different from Bayer
alumina, 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 H
2
SO
4
is added to the digest [52]. The combination of acids eliminated the need to
roast the clay. Other processes use H
2
SO
4
, H
2
SO
3
, HNO
3
, or NH
4
HSO
4
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 modifications, 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 their
composition, require different technology. Alunite, K
2
SO
4
Al
2
(SO
4
)
3
2Al
2
O
3
6H
2
O [12588-67-9],
has been used commercially in Russia. Both H
2
SO
4
and K
2
SO
4
are useful byproducts of alumina
production by this method. The alunite is heated to drive off the hydrated water; additional heating
under reducing conditions decomposes the aluminum sulfate without adversely affecting alumina
recovery. The solid residue from the roast is a mixture of K
2
SO
4
, Al
2
O
3
, and gangue. The K
2
SO
4
is
dissolved in water and recovered. Alumina is extracted from the gangue in a modification of the Bayer
process. In other approaches using alunite, the solutions are kept acidic so the alumina is recovered as a
salt [59].
Dawsonite, Na
2
O Al
2
O
3
2 CO
2
2 H
2
O [12011-76-6], is found in some oil shales. The temperatures
used to recover the oil from the shale decompose the dawsonite to NaAlO
2
, which is soluble in dilute
NaOH. The Al(OH)
3
and Na
2
CO
3
can be recovered from the solution by carbonation. The economics
are such that recovery of the oil must be competitive before mining and byproduct recovery can be
considered.
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5. Metallurgical Alumina
Aluminum production is the principal application for alumina; more than 92% of world alumina
production is used for this purpose. The property requirements for commercial metallurgical alumina
are therefore of considerable importance to the alumina industry. Specifications have responded to
changes in energy costs, aluminum cell design, cell gas scrubbing techniques, environmental
regulations, working conditions in smelters, and the technology for alumina calcination. In general,
there has been a shift away from relatively small-particle-size, highly calcined, "floury" alumina to a
coarse, free flowing, dust-free, less calcined, "sandy" alumina of narrower particle sizing and higher
chemical purity ( Aluminum).
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5.1. Alumina Properties Required for Smelting
Five developments have had a significant impact on alumina properties.
Cell Design. New, high current efficiency, prebaked anode cells with automatic center-feed systems
require that the alumina be consistent, with trouble-free handling properties to insure proper conveying
and volumetric metering from the feeder. These criteria are best met by a free-flowing, moderate- to
low-calcined alumina with relatively coarse and narrow particle size distribution.
Cell Gas Dry Scrubbing. The use of dry scrubber systems employing cell-feed alumina as adsorbent
for fluorides in effluent gas from the cells dictates other requirements for metallurgical alumina:
1) High adsorption capacity for hydrogen fluoride. This property is closely related to the specific
surface area of the alumina, which is higher for the lower calcined aluminas.
2) Attrition resistance.
3) Free flowability.
4) Higher chemical purity to compensate for capture in the dry scrubber of impurities which are
recycled to the cell.
Pot Room Working Conditions. Use of low-calcined, high surface area alumina as a cover for the cell
bath reduces fluoride evolution within the pot room. Working conditions in the smelter are degraded by
dust caused by fine particles of alumina. Reduction of the fines fraction (<44 m) in the alumina and
high attrition resistance are important for reducing dust.
Use of Stationary Calciners and Pneumatic Handling Systems for Alumina. The replacement of
rotary alumina kilns by the energy-efficient stationary calciners has resulted in producing a different
type of calcined alumina for smelter feed. This difference is reflected in the interrelationship between
degree of calcination (measured by the mass loss on ignition), specific surface area, and the o-Al
2
O
3

content [60].
The strength of the alumina particles has become of concern not only because of relatively higher
breakdown in the stationary calciners, but also because of attrition occurring in pneumatic unloading
and conveying equipment and in fluid-bed dry-scrubbing systems. The generation of fine particles in
such equipment, apart from causing unacceptable dusting conditions in the smelters, often results in
troublesome segregation problems in alumina storage bins and bunkers.
Electrolyte Composition and Temperature. The trend to operate cells at lower temperatures with
electrolyte having a lower bath ratio (NaF:AlF
3
) has decreased the solubility and rate of dissolution of
alumina in the electrolyte. The rate of dissolution is greater for aluminas having higher surface areas
and low content of o-Al
2
O
3
. Both properties can be achieved by a low degree of calcination.
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5.2. Typical Specifications for Metallurgical Alumina
The considerations discussed in Section 5.1. Alumina Properties Required for Smelting have
contributed to the evolution of the general specifications used in production and international trading
(Table (8)). These values are only representative and considerable variation exists in actual practice
depending on price, availability, smelting practices, and many other factors. Consistency of quality is a
major consideration.
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6. I ndustrial Alumina Chemicals
Alumina, in various forms, is one of the inorganic chemicals produced in greatest volume today.
Although production of aluminum metal currently consumes ca. 90% of all alumina, an increasing
amount is being applied in the chemical industry for fillers, adsorbents, catalysts, ceramics, abrasives,
and refractories. With the development and growth of applications and markets for alumina chemicals,
all the major alumina producers have, over the years, converted a part of their capacity to produce
various alumina chemicals. In fact, some of the older, smaller alumina refining plants have been totally
converted to alumina chemicals production in order to be economically viable. Chemical uses account
for nearly 8% of the world production.
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6.1. Aluminum Hydroxides
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Aluminum hydroxides constitute a versatile group of industrial chemicals. Important uses requiring
large quantities are as fillers in plastic and polymer systems and for the production of aluminum
chemicals. A moderate amount is used for the production of alumina-based adsorbents and catalysts.
Aluminum hydroxide meets most of the requirements for an effective filler: white or near-white color;
large volume production base, resulting in price and supply stability; consistency of physical and
chemical properties; a wide range of particle size distributions; chemical inertness; and nontoxicity.
However, its increasing popularity as a plastics filler is strongly related to its fire-retardant and smoke-
suppressant properties, which justify the somewhat higher price compared with calcium carbonate and
other mineral fillers. Aluminum hydroxide acts as a fire retardant by adsorbing heat through
endothermic dehydration and dilution of pyrolytically produced combustion gas by the released steam.
Dehydration and water release processes become significant at temperatures above 500 K. The smoke-
inhibiting activity of aluminum hydroxide filler has been attributed to promotion of solid-phase
charring in place of soot formation. Although offering these desirable features, aluminum hydroxide
has certain disadvantages that impose some limitations on its uses as a filler. Like other nonreinforcing
mineral fillers, it generally lowers strength. Because it undergoes thermal decomposition, it is not
suitable for processing above 500 K. These factors are responsible for the larger use of aluminum
hydroxide in latex carpet backings and in glass-reinforced polyesters, where processing temperatures
below about 480 K generally are used. These are also chemically cross-linked or fiber-reinforced
systems, in which loss of strength caused by a nonreinforcing filler may not be very important.
Aluminum hydroxide filler has been used less extensively in thermoplastics, e.g., poly(vinyl chloride)
and polyethylene, and elastomeric materials. For use as a filler, the crystalline aluminum hydroxide
from the Bayer process is dried and ground to particles 10 m size. Special grades with increased
whiteness and a variety of both particle size ranges and chemical purity also are available
commercially.
Fine, precipitated aluminum hydroxide having a uniform particle size (~1 m) is used in paper making
as a filler pigment and as a coating. As a filler, it disperses rapidly with low sedimentation. Improved
printing properties are reported for the hydroxide-filled paper. The application of fine, platy aluminum
hydroxide as a paper coating is well established in the paper industry. It gives a coating of high
brightness, opacity, and gloss ( Paper and Pulp).
Technical aluminum hydroxide obtained from the Bayer process is 99.5% pure. It dissolves readily in
strong acids and bases. For these reasons, aluminum hydroxide is the preferred raw material for the
production of a large number of aluminum compounds. These include pure, iron-free aluminum sulfate
(used in the paper industry and for water purification), aluminum fluoride, synthetic zeolites, and
sodium aluminate. Aluminum hydroxide also is used in the glass industry and in cosmetic and
pharmaceutical preparations. An important cosmetic use of aluminum hydroxide is in toothpaste. The
mildly abrasive hydroxide cleans and polishes teeth.
The price of aluminum hydroxides ranged from $0.20 to $0.60 per kg in 1990, the price range
reflecting the cost of additional processing of the usual Bayer process product to suit application
requirements. These include grinding, higher purity, classification, surface treatment, etc.
Pharmaceutical-grade gel hydroxides were at the top of the price range.
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6.2. Adsorbent and Catalytic Aluminas
Activated aluminas represent another group of technically important alumina chemicals. Principal uses
are as drying agents, adsorbents, catalysts, and catalyst carriers. These products are obtained by thermal
dehydration of different aluminum hydroxides in the 5201070 K temperature range (see Section 1.5.
Thermal Decomposition of Aluminum Hydroxides).
6.2.1. Preparation of Activated Aluminas
Bayer aluminum hydroxide is the chief source of commercial activated alumina products. Powder
forms of activated alumina are produced by heating the hydroxide directly at 5751825 K in ovens or
in rotary or fluidized-bed calciners. The products have surface areas of 200350 m
2
/g and losses on
ignition of 312 wt% (at 5751473 K). Such products are used as decolorizing agents for organic
chemicals and as starting material for the production of aluminum fluoride ( Fluorine Compounds,
Inorganic). Other uses include chromatographic and catalytic applications in organic chemistry.
Granular activated alumina produced from Bayer plant crust is one of the oldest commercial forms of
this product and still is used widely. A flow sheet of the production process is shown in Figure (20).
The activated material is a hard, nondusting product. Table (9) lists some properties of a commercial
product of this type (Alcoa F-1). A similar granular product has been produced by compacting Bayer
hydroxide by mechanical pressure (Martinswerk GmbH, Federal Republic of Germany). The process
utilizes a roll-type compactor. The product from the compactor is broken up and sieved to the required
size fractions and activated at 675875 K in a rotary calciner.
Fast dehydration of Bayer aluminum hydroxide, either by vacuum or by exposure to high-temperature
gas (10501300 K) for a few seconds, has been used for the production of ball-shaped, activated
alumina having properties superior to the granular product. This process results in the formation of
nearly amorphous -Al
2
O
3
. The product is finely ground and using water as binder, formed into
spherical agglomerates in a rotating pan agglomerator. Rehydration of -Al
2
O
3
with water leads to
crystallization of bayerite, causing the agglomerates to harden. Reactivation of the hard balls at 675
775 K produces the activated product (520 mm in diameter) having a surface area of 320380 m
2
/g.
Alumina gels also have been used for the manufacture of activated aluminas. These gels are produced
by neutralization of aluminum sulfate or ammonium alum by NH
4
OH, or from sodium aluminate by
neutralization with acids, CO
2
, NaHCO
3
, and Al
2
(SO
4
)
3
. The gelatinous aluminum hydroxide
precipitate is filtered and thoroughly washed and dried. The dried product is activated, milled, and
agglomerated to a spherical product. Other forming processes, such as extrusion, pelletizing, and
tableting, also can be used. The product is finally activated at 675875 K to a loss on ignition value of
about 6%. Although gels of various textures can be prepared, the usual industrial adsorbent products
have very small pores (less than 4 nm in diameter) and surface areas in the range of 300400 m
2
/g. A
flow sheet of a manufacturing process is shown in Figure (21). Table (9) reports data on a commercial,
gel-based product (Alcoa H-151).
Aluminum oxide hydroxide (boehmite), a byproduct from the Ziegler process for linear alcohol
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
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
is claimed to serve as its own binder when peptized with glacial acetic acid. The extrudate is cut to the
required size, dried, and activated at 775875 K. The surface area of the activated product is 185250
m
2
/g. Commercial bayerite also has been used to produce activated alumina; the product is preferred in
some catalytic applications.
6.2.2. Adsorbent Applications
A major application of activated alumina is in the field of adsorption, where its high surface area, pore
structure, strength, and chemical inertness favor its use. The alumina performs important technical
functions, such as gas and liquid drying, water purification, and selective adsorption in the petroleum
industry.
Gases that have been dried successfully by alumina desiccants are:
acetylene cracked gas hydrogen oxygen
air ethane hydrogen chloride propane
ammonia ethylene hydrogen sulfide propene
argon freon methane sulfur dioxide
carbon dioxide furnace gas natural gas
chlorine helium nitrogen
In many applications an alumina desiccant can dry gas to a lower dew point than any other
commercially 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).
Moist gas usually is dried by passing it through a column (or tower) packed with the adsorbent.
Adsorption of water on activated alumina is strongly exothermic, releasing between 45 and 55 kJ of
heat per mole of water adsorbed. This factor must be considered in the design of the drying tower. Both
granular and spherical forms of activated alumina can be used in desiccant beds. Sizes from 2 to 20 mm
are available commercially. The granular products have lower surface areas and their application is
based on low cost per kilogram, low water load, and low stream pressure. Spherical products, produced
by either the gel or the fast dehydration processes, have larger surface areas, a narrower pore structure,
and a high adsorption capacity, and they are relatively more expensive than the granular variety. The
spherical kind usually is specified for high-pressure, high-moisture removal duties. The alumina
desiccant is regenerated by passing a current of hot, dry gas (475 K) through the bed, usually
countercurrent to the main gas flow.
Liquids that can be dried with activated alumina include aromatic hydrocarbons, higher molecular mass
alkanes, gasoline, kerosene, cyclohexane, power system coolants, lubricants, and many halogenated
hydrocarbons. Liquids that are highly adsorbed on alumina (e.g., ethanol and methanol), react or
polymerize in contact with activated alumina. Those containing components that tend to deposit on the
alumina surface cannot be dried by activated alumina. Regeneration schemes for liquid dehydration
units are varied and depend on the liquid being dried. In some applications the liquid being dried is
vaporized, heated, and passed through the desiccant bed to adsorb water. Hot, dry gases also are used
for regeneration.
An evolving application of activated alumina is in water purification. Several important contaminants
have been removed from water successfully and economically in pilot plants as well as in large-scale
treatment plants. These include reduction of fluoride concentration in drinking water and in some
industrial effluents, and removal of color and odor from effluent water from dye works and paper mills.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Removal of phosphate and arsenic also has been investigated.
Activated alumina can be used to separate one or more components from a gas or liquid stream by
taking advantage of differences in adsorption or desorption kinetics. For example, a short cycle process
has been used to recover heavy hydrocarbons from a stream of lighter hydrocarbons. Often a
regeneration scheme can be devised that permits cyclic use of the alumina. In other instances, such as
removal of catalyst in polyethylene and hydrogen peroxide production, it is more economical not to
recycle the alumina.
6.2.3. Catalytic Applications
Alumina is used in many industrial catalytic processes, both as the catalyst and as a support for
catalytically active components. In many instances, the alumina support contributes to catalytic activity
and so assumes an essential role in the catalyst system. Other catalytic uses of alumina take advantage
of its strength, heat resistance, and inertness.
Although the common adsorbent aluminas derived from Bayer hydroxide have many catalytic
applications, high-purity materials (e.g., boehmite from the Ziegler process for linear alcohol
production) are sometimes preferred. Because of the lower cost of Bayer process-based products, such
techniques as water and acid washing of the activated product have been employed to reduce the alkali
(Na
2
O) content of the Bayer material. The sodium oxide is known to have a negative influence in many
catalytic processes. Catalyst-forming methods include tableting, pelletizing, compacting, ball forming
(agglomeration), and extrusion. Such factors as purity, surface area, pore volume, and size distribution,
and rate of deactivation influence catalyst performance and selectivity. In addition, crushing strength
and resistance to attrition of the catalyst pellets are important considerations in practical operation of
catalytic reactors. Although these physical aspects of alumina catalysts are well characterized, the
surface structure and chemistry responsible for catalytic activity still remains unclear. Many
investigators have attributed catalytic activity to the intrinsic acidity of the surface of activated
alumina. First, the combination of two neighboring OH

groups to form water during the dehydration


process leaves behind an exposed Al
3+
ion, which, because of its electron deficiency, behaves as a
Lewis acid site. In addition, hydroxyl groups are retained during thermal decomposition of aluminum
hydroxide (see Section 1.5. Thermal Decomposition of Aluminum Hydroxides). These OH

ions on the
surface may act as proton donors (Brnsted acids). These Lewis and Brnsted acid sites have been
looked upon as the active catalytic centers. Further "defect" structures are formed with increasing
degree of dehydration [56]. Of the types of defects created during dehydration, those assumed to have
the greatest catalytic importance are the triplet vacancies. They provide unusual exposure of the
aluminum ions in the underlying layer and constitute strong acid sites.
Catalytic applications of alumina are extensive. Important industrial processes employing alumina as a
catalyst by itself include alcohol dehydration and the Claus process for sulfur recovery ( Sulfur).
Dehydration of alcohols over activated alumina is one of the oldest catalytic processes. Typical
reaction conditions for olefin production are 575675 K and atmospheric pressure. Lower
temperatures favor the formation of ethers. The most suitable aluminas for alcohol dehydration
catalysis are those that have large surface areas (150200 m
2
/g) and possess good thermal and
hydrothermal stability. Coke formation occurs over a period of several hundred operating hours and the
catalyst must be regenerated by burning off the carbon with hot air at 773873 K.
The largest present-day catalytic application of activated alumina itself is in the Claus process, which is
used to recover sulfur from hydrogen sulfide (H
2
S).
2 H
2
S +SO
2
2 H
2
O +3 S AH = 147 kJ
The reaction is carried out catalytically in two or more conversion stages using alumina catalysts.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Reaction temperature in the first stage is around 625 K. At this temperature, the conversion of H
2
S is
only about 65%. Subsequent lower temperature catalytic stages are used to further reduce the H
2
S
concentration. Spherical, high-strength activated alumina catalysts are used in the Claus converters.
Service life as high as 5 years has been reported. Deactivation of the alumina catalyst occurs by
sulfation, thermal aging, and carbon and/or sulfur deposition. Regeneration of Claus catalyst involves
removal of sulfur and burning off of carbon deposits.
Alumina-supported catalysts are used extensively in the petroleum and chemical industries. In general,
the petroleum industry catalysts have high surface area and high porosity; the support is mostly
activated alumina. On the other hand, many typical chemical process catalysts (e.g., ammonia
synthesis, steam reforming) are characterized by lower surface area (<20 m
2
/g) and are nonporous or
have very large diameter pores. The carrier in this case is inert and consists mostly of calcined or
sintered alumina products.
Two different methods have been used commonly for preparation of alumina-supported catalysts:
impregnation and coprecipitation. The alumina support used in the impregnation process generally has
been formed into its final shape (extrudates, tablets) prior to the impregnation step. Impregnation with a
salt solution of the active species is then carried out, followed by drying and thermal decomposition of
the salt. In the coprecipitation procedure, hydroxides of aluminum together with the active component
are precipitated from a salt solution by neutralization with ammonia or alkali. The washed precipitate is
dried, powdered, and processed (e.g., by extrusion) to the desired shape and finally activated by
thermal dehydration. The coprecipitation method is used when the active species must be present in
high concentrations or when more uniform distribution of the active component is desired.
The technical and patent literature contains innumerable examples of the use of alumina as a catalyst
support. Some important examples are the catalytic dehydration of n-butane to butadiene (used in
synthetic rubber), using a chromia-impregnated alumina catalyst; molybdenumalumina catalysts,
used in hydrorefining operations (e.g., desulfurization) in petroleum refining; and pelleted catalysts
containing platinum, palladium, and rhodium on an alumina base, used in automobile exhaust catalytic
converters.
United States production of adsorbent-grade activated aluminas, both granular and spherical, amounted
to nearly 250000 t in 1990. Price of the cheaper, granular product was quoted around $ 0.400.50 per
kg. Price of the spherical product ranged from $ 0.55 to $0.65 per kg. Total catalytic applications of
alumina in the United States were estimated to be around 400000 t in 1990. Price of preformed alumina
for catalytic applications ranges from $ 0.60 to $ 4.00 per kg, depending on source and purity. Alumina
-based Claus catalyst was priced between $ 3.00 and $ 3.50 per kg.
Continued ...
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References
7. Ceramic Uses of Alumina
Alumina is used extensively as a ceramic material ( Ceramics, Advanced Structural Products).
Products range from relatively low-calcined grades of polishing aluminas to the extremely hard, fused
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
alumina and synthetically produced sapphire. The characteristics that make alumina valuable in
ceramic applications are high melting point (2325 K), hardness (9 on the Mohs scale), strength,
dimensional stability, chemical inertness, and electrical insulating ability. These, together with
availability in large quantities at moderate prices, have led to extensive and varied uses of alumina as a
ceramic material.
Continued ...
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References
7.1. Calcined Alumina
Ceramic aluminas are generally produced by calcining Bayer aluminum hydroxide at temperatures high
enough for the formation of o-Al
2
O
3
. By control of calcination time and temperature and by the
addition of mineralizers, such as fluorine and boron, the crystallite size in the calcined product can be
varied from 0.2 to 100 m. These calcined aluminas can be categorized broadly according to their
sodium content. There are two general types: those having about 0.5% Na
2
O and low-soda grades with
a content <0.1%.
Reactive alumina is a material manufactured by dry grinding calcined alumina to particle sizes smaller
than 1 m. The large surface area associated with very fine particles and the high packing densities
obtainable considerably lower the temperatures required for sintering.
Tabular aluminas are manufactured by grinding, shaping, and sintering calcined alumina. The thermal
treatment at 19002150 K causes the oxide to recrystallize into large, tabular crystals of 0.20.3 mm.
Continued ...
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References
7.2. Fused Alumina
For ceramic applications and for the production of abrasives, fused aluminas are manufactured by
melting a suitable raw material in an electric arc furnace ( Abrasives). Calcined alumina from the
Bayer process is used as a starting material for the highest quality fused alumina. Bauxites with varying
levels of iron oxide, silicates, and titanium minerals are melted to produce the brown or less pure black
qualities.
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Continued ...
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References
8. Toxicology and I ndustrial Hygiene
For a discussion concerning the toxicology and industrial hygiene of aluminum oxides, Aluminum -
9. Toxicology and Occupational Health.
Continued ...
Title page
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9. References
[1] H. Ginsberg, F. W. Wrigge: Tonerde und Aluminium, Teil 1, Die Tonerde, W. De Gruyter,
Berlin 1964.
[2] H. Ginsberg, K. Wefers: Aluminiumund Magnesium, vol. 15, Die Metallischen Rohstoffe, Enke
Verlag, Stuttgart 1971.
[3] K. Wefers, C. Misra: Oxides and Hydroxides of Aluminum, Alcoa Technical Paper no. 19,
revised, Pittsburgh 1987.
[4] T. G. Parson: The Chemical Background of the AluminumIndustry; Lectures, Monographs, and
Reports, no. 3, The Royal Institute of Chemistry, London 1955.
[5] P. Barrand, R. Gadeau: l'Aluminium, part 1, Editions Eyrolles, Paris 1964.
[6] A. N. Adamson, E. J . Bloore, A. R. Carr: Basic Principles of Bayer Process Design, Extractive
Metallurgy of Aluminum, vol. 1, Interscience Publishers, New York 1963.
[7] A. N. Adamson: "Aluminum Production Principles and Practice," The Chemical Eng. (London),
J une 1970, 156171.
[8] S. I. Kuznetsov, V. A. Derevyankin: The Physical Chemistry of Alumina Production by the
Bayer Process, Moscow 1964.
[9] W. H. Gitzen: Alumina as a Ceramic Material, The Amer. Cer. Society, Columbus, Ohio 1970.
[10] C. Misra: Industrial Alumina Chemicals, ACS Monograph 184, The Amer. Chem. Society,
Washington, DC 1986.
[11] L. J acob, J r. (ed): Bauxite, The Amer. Chem. Society, Westerville, Ohio 1990.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
[12] L. D. Hart (ed): Alumina Chemicals Science and Technology Handbook, Society Of Mining
Engineers (AIME), New York 1984.
[13] J . Bhm, H. Niclassen, Z. Anorg. Allg. Chem. 132 (1923) 1.
[14] R. Fricke, Z. Anorg. Allg. Chem. 175 (1928) 249; 179 (1929) 287.
[15] T. G. Gedeon, Acta Geol. Acad. Sci. Hung. 4 (1956) 95.
[16] R. A. Van Nordstrand, W. P. Hettinger, C. Keith, Nature (London) 177 (1956) 713.
[17] H. Saalfeld, Neues J ahrb. Mineral. Abh. 95 (1960) 1.
[18] H. Ginsberg, W. Httig, H. Stiehl, Z. Anorg. Allg. Chem. 309 (1961) 233; 318 (1962) 238.
[19] K. Wefers, Naturwissenschaften 49 (1962) 204.
[20] K. R. Poppelmeier, S. J . Hwu, Inorg. Chem. 26 (1987) 32973306.
[21] U. Hauschild, Z. Anorg. Allg. Chemie 324 (1963) 15.
[22] B. C. Lippens, Ph. D. Dissertation, University Delft (1961).
[23] H. D. Megaw, Z. Kristallogr. 87 (1934) 185.
[24] F. J . Ewing, J . Chem. Phys. 3 (1935) 203.
[25] W. R. Busing, H. A. Levy, Acta Crystallogr. 11 (1958) 798.
[26] O. Glemser, E. Hartert, Z. Anorg. Allg. Chem. 283 (1956) 111.
[27] W. H. Bragg, J . Chem. Soc. 121 (1922) 2766.
[28] A. W. Laubengayer, R. S. Weiss, J . Am. Chem. Soc. 65 (1943) 247.
[29] G. Ervin, E. F. Osborn, J . Geol. 59 (1951) 381.
[30] G. C. Kennedy, Am. J . Sci. 257 (1959) 563.
[31] A. Neuhaus, H. Heide, Ber. Dtsch. Keram. Ges. 42 (1965) 167.
[32] K. Wefers, Erzmetall 20 (1967) 13, 71.
[33] H. Schwiersch, Chem. Erde 8 (1933) 252.
[34] A. H. Carim et al., J . Am. Ceram. Soc., 80 (1997) 26772680.
[35] W. Feitknecht, A. Wittenbach, W. Buser: 4th Symposiumon Reactivity of Solids, Elsevier,
Amsterdam 1961, p. 234.
[36] F. Freund, Ber. Dtsch. Keram. Ges. 42 (1965) 23; 44 (1967) 141.
[37] J . M. McHale et al., Science 277 (1977) 788791.
[38] K. Wefers, Erzmetall 17 (1964) 583.
[39] H. C. Stumpf, A. S. Russell, J . W. Newsome, C. M. Tucker, Ind. Eng. Chem. 42 (1950) 1398.
[40] I. Valeton: "Bauxites," Dev. Soil Sci. 1, (1972).
[41] J . G. deWeisse: Les Bauxites de l'Europe Centrale, Univ. Lausanne 1948.
[42] V. Z. Zans, Geonotes 5 (1959) 123.
[43] M. E. Roch: "Les bauxites du Midi de la France," Rev. Gen. Sci. Pures Appl. Bull. Assoc. Fr.
Av. Sci.66 (1958) no. 5/6, 151156.
[44] H. Erhart: "La Gense des Sols," Evolution des Sciences, Masson, Paris 1956.
[45] G. Bardossy: Bibliographie des Travaux Concernant les Bauxites, ICSOBA, Paris 1966.
[46] U.S. Geological Survey, Mineral Commodity Summaries, J anuary 1998.
[47] Nippon Light Metal Col., DE 2 807 245, 1977 (M. Kanehara, A. Kainuma, M. Fujiike).
[48] P. Basu, "Reactions of Iron Minerals in Sodium Aluminate Solutions," Light Met. (New York)
1983, 8398.
[49] D. K. Grubbs, S. C. Libby, J . K. Rodenburg, K. Wefers, J . Geol. Soc. J am. 4 (1980) 176186.
[50] K. Yamada, T. Harato, H. Kato, Light Met. (N.Y.) 1981, 117128.
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
[51] C. Misra, Travaux ICSOBA 24 (197) 194204.
[52] UNEP/UNIDO Workshop Envir. Asp. Alumina Prod., Paris 1981.
[53] K. Bielfeldt, K. Kmpf, G. Winkhaus, Erzmetall 29 (1976) 120125.
[54] The Aluminum Association, Inc., N.Y., Report no. 4, Sept. 15, 1981.
[55] G. Lang, K. Solymar, J . Steiner, Light Met. (N.Y.) 1981, 201214.
[56] H. W. St. Clair, D. A. Elkins, W. M. Mahan, R. C. Merritt, M. R. Howcroft, M. Hayashi,
Bulletin 577, U.S. Bureau of Mines, 1959.
[57] K. B. Bergston, Light Met. (N.Y.) 1979, 217282.
[58] N. Gjelsvik, Light Met. (N.Y.) 1980, 133148.
[59] V. S. Sazlin, A. K. Zapolskii, Tsvetn. Metall. UDK 669.712.2 (1968) 64.
[60] E. Barrilon, Erzmetall 31 (1978) 519522.
[61] H. Knzinger, P. Ratnasamy, Catal. Rev. Sci. Eng. 17 (1978) 3170.
first occurrence in article
Aluminum Oxide - Table 1
Mineralogic properties of oxides and hydroxides [3]
Phase Refractive index n
D
20
Cleavage Brittleness Mohs Luster
hardness
o | 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
c e Average
Corundum 1.7604 1.7686 none tough when compact 9 pearly adamantine
first occurrence in article
Aluminum Oxide - Table 2
Structural properties of oxides and hydroxides [3]
Phase Formula Crystal system Space Molecules Unit axis length, Angle Density
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
group per unit 10
1
nm
cell a b c g/cm
3
Gibbsite Al(OH)
3
monoclinic C
2
5
h
4 8.68 5.07 9.72 9434' 2.42
Gibbsite Al(OH)
3
triclinic 16 17.33 10.08 9.73 9410' 9208' 900'
Bayerite Al(OH)
3
monoclinic C
2
5
h
2 5.06 8.67 4.71 9016' 2.53
Nordstrandite Al(OH)
3
triclinic C
i
1
4 8.75 5.07 10.24 10920' 9740' 8820'
Boehmite AlO(OH) orthorhombic D
2
1
h
7
2 2.868 12.227 3.700 3.01
Diaspore AlO(OH) orthorhombic D
2
1
h
6
2 4.396 9.426 2.844 3.44
Corundum Al
2
O
3
hexagonal (rhomb.) D
3
6
d
2 4.758 12.991 3.98
first occurrence in article
Aluminum Oxide - Table 3
Principal chemical constituents of various bauxites, wt%
Country and location Al
2
O
3
SiO
2
Fe
2
O
3
TiO
2
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
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Indonesia
Bintan 53.5 3.9 12.1 1.6 29.2
J amaica
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
first occurrence in article
Aluminum Oxide - Table 4
World bauxite reserves and production, 10
3
t [46]
Country Mine production Reserves
1996 1997
United States n.a. n.a. 40000
Australia 43100 43500 7900000
Brazil 9700 9700 2900000
China 6200 7000 2000000
Guinea 14000 14000 900000
Guyana 2000 2000 900000
India 5100 5500 200000
J amaica 11829 12000 2000000
Russia 3300 3300 200000
Surinam 4000 4000 600000
Venezuela 5600 5600 350000
Other countries 8928 8900 4400000
World total (rounded) 114000 115000 28000000
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first occurrence in article
Aluminum Oxide - Table 5
World alumina production, 10
3
t Source: Roskill's Metals Databook 1997)
Country Production
1996 1997
Australia 13008 13349
Brazil 2147 2800
Canada 1064 1100
China 2080 n.a.
France 425 430
Germany 994 1000
Greece 630 630
Guinea 630 622
Hungary 353 n.a.
India 1650 1660
Ireland 1186 1300
Italy 857 880
J amaica 3030 3200
J apan 743 750
Spain 1095 1100
Surinam 1579 1600
Turkey 172 170
United Kingdom 110 110
United States 4530 4780
Venezuela 1641 1700
Yugoslavia 150 300
World total 43600 45000
first occurrence in article
Aluminum Oxide - Table 6
Commercial digestion conditions
Bauxite type Temperature, K c
NaOH
, g/L Final c
Al
2
O
3
, g/L
gibbsitic 380 260 165
415
105145 90130
boehmitic 470 150250 120160
510
105145 90130
diaspore* 535 150250 100150
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
* CaO is added to digests to accelerate dissolution of diaspore.
first occurrence in article
Aluminum Oxide - Table 7
Dilution balance
Inputs Losses
residue wash evaporation
sand wash
Al(OH)
3
wash heat interchange flash
free moisture in bauxite Al(OH)
3
to calcination
water in gibbsite and boehmite free water with Al(OH)
3
injected steam water with residue
purge water vapor from solution surfaces
sodium hydroxide
cleanup water (maintenance)
uncontrolled dilutions
first occurrence in article
Aluminum Oxide - Table 8
Typical properties of metallurgical alumina
Physical property
Particle size distribution, wt%
+100 mesh (Tyler) <5
+325 (44 m) >92
325
<8
Bulk density, kg/L
loose
0.951.00
packed
1.051.10
Specific surface area, m
2
/g 5080
Moisture (to 573 K), wt% <1.0
Loss on ignition (5731473 K), wt% <1.0
Attrition index (modified ForsytheHertwig method) increase in <44 m particles 415 wt%
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
o-Al
2
O
3
content (by optical or X-ray method), % <20
Chemical analysis wt%
Fe
2
O
3
<0.015
SiO
2
<0.015
TiO
2
<0.004
CaO
<0.040
Na
2
O
<0.400
first occurrence in article
Aluminum Oxide - Table 9
Typical properties of Alcoa activated aluminas
F-1 H-151 S-100
Al
2
O
3
, % 92 90 95
Na
2
O, % 0.58 1.6 0.35
SiO
2
, % 0.12 2.0 0.03
Fe
2
O
3
, % 0.06 0.03 0.05
Loss on ignition, % 7 6 5
Loose bulk density:
g/cm
3
0.83 0.82 0.80
lb/ft
3
52 51 50
Packed bulk density:
g/cm
3
0.85 0.85 0.75
lb/ft
3
55 53 47
Pore characteristics and surface area of typical Alcoa activated aluminas
Helium (true) density, g/cm
3
3.25 3.40 3.15
Mercury (particle) density, g/cm
3
1.42 1.38 1.24
Micro pore volume (pores <3.5 nm), cm
3
/g 0.017 0.023 0.012
Macro pore volume (pores >3.5 nm), cm
3
/g 0.023 0.020 0.037
Total pore volume, cm
3
/g 0.40 0.43 0.49
Total porosity, % 56.3 59.4 60.6
Pore diameter at 50% total pore volume, nm 17.7 3.5 4.7
Primary pore size range, nm
010000 040 0500
BET surface area, m
2
/g 250 360 260
Pore diameter, nm
10
6
10
7
0.0031 0.0003 0.0000
Pore volume, cm
3
/g
10
5
10
6
0.0045 0.0001 0.0001
10
4
10
5
0.0059 0.0001 0.0004
10
3
10
4
0.0029 0.0004 0.0033
10
2
10
3
0.0045 0.0093 0.0047
3510
2
0.0021 0.0099 0.0289
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
235 0.0165 0.0232 0.0115
0.0395 0.0433 0.0489
first occurrence in article
Aluminum Oxide - Figure 1
Classification of aluminum hydroxides
(All figures courtesy of Aluminum Company of America)
first occurrence in article
Aluminum Oxide - Figure 2
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Somatoids of bayerite
first occurrence in article
Aluminum Oxide - Figure 3
The Al
2
O
3
H
2
O system
Dashed lines [21], solid lines [22], [28]
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 4
Gibbsite heated to 573 K
first occurrence in article
Aluminum Oxide - Figure 5
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Specific surface area, loss on ignition (LOI), and density of heated Al(OH)
3
first occurrence in article
Aluminum Oxide - Figure 6
Decomposition sequence of aluminum hydroxide
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 7
Bayer process flow sheet
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 8
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Phase diagram Na
2
OAl
2
O
3
H
2
O
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 9
High-temperature digestion and heat recovery
first occurrence in article
Aluminum Oxide - Figure 10
Tube digester
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
a) Piston pump; b) Heat; c) Condensate; d) Flow control valve; e) Steam
first occurrence in article
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
first occurrence in article
Aluminum Oxide - Figure 12
Flows at stage n in countercurrent decantation
(O=overflow; U=underflow)
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 13
Generalized solubility curve
first occurrence in article
Aluminum Oxide - Figure 14
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Technical aluminum hydroxide (gibbsite) 200
first occurrence in article
Aluminum Oxide - Figure 15
Effect of temperature on precipitation
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ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
first occurrence in article
Aluminum Oxide - Figure 16
Al
2
O
3
concentration profiles in batch and continuous precipitation
first occurrence in article
Aluminum Oxide - Figure 17
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
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
first occurrence in article
Aluminum Oxide - Figure 18
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Lime/soda sinter process flow sheet
first occurrence in article
Aluminum Oxide - Figure 19
Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release Wiley-VCH. Weinheim. Germany.
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Generalized acid process flow sheet
first occurrence in article
Aluminum Oxide - Figure 20
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Flow sheet for production of activated alumina from Bayer plant crust
first occurrence in article
Aluminum Oxide - Figure 21
Production of gel-based activated alumina
first occurrence in article
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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ALUMINUM OXIDE - Bayer Process (L. Keith Hudson, Chanakya Misra, Anthony J . Perrotta, Karl Wefers, F. S. Williams)
Aluminum Oxide - Figure 22
Static water adsorption capacity of typical commercial activated aluminas at 25 C (298 K)
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