Bayer Process Chemistry

Dr. M. Coley
 Bauxite - Appearance
Appearance
red soil – Jamaica; Australia
white rock – Europe; Guyana
Often yellow or black soil
 Bauxite - Appearance

Bauxite is any ore of Al which may be processed

economically via the Bayer process to recover alumina.
Bauxite - Appearance
 Bauxite
Location:
• often found near limestone deposits

• possibly deposited by underground streams

• rising of water table

Major Theories
Alluvial deposit theory – plateau bauxite

Valley bauxite – weathering of limestone

Origin
weathering of igneous rocks
chemical, physical & microbial processes
ultisol; Na, K, Ca, Fe & SiO2 dislodged
Bauxite Origin Diagram
 Bauxite Characterization
XRD – estimates content of each bauxite phase (b. Al2O3)

XRF – estimates metal impurity content (SiO2, ZnO, P2O5)

- {both methods analyze dry fused samples}

ICP & AAS - alternative analytical techniques to XRF

LOI & TOC – Loss on Ignition & total organic carbon

TAA – estimates % Available Al2O3

 XRD of
Bauxite

XRD of
Red Mud
 Evaluation of Bauxites
 Convenience of location- rail, road, ropeway

 Ease of mining – open pits, underground

 Mineralogy – process design, operation

critical: Al2O3, SiO2, Fe2O3, TiO2
less important: P2O5, ZnO, MnO2, Organics

 Nature of bauxite particles – crushing dynamics

 Size of bauxite deposits

 Table 2.1.1.1: Composition of bauxite in major
producing countries

Australian Guinea
Oxide (Darling Guyana (Sangaredi Jamaica
Range) District)

% Al2O3 38-46 55-60 57-60 45-49

% Fe2O3 11-16 <3 2-4 17-22

% SiO2 10-23 2-5 <1 0.8-8

% TiO2 ~4 - - 2.5

(Kogel et al., 2006)

 Table 2.1.5.1: Minerals present in Jamaican
bauxites
(Strahl, 1971; Hill, 1973)

Essential Varietal Accessory

Gibbsite (Al) Quartz (Si) Calcite (Ca)
Boehmite (Al) Kaolinite (Si Illmenite (Fe, Ti)
Hematite (Fe) Hydroxyapatite (Ca, Magnetite (Fe)
P)

Goethite (Fe) Rutile (Ti) Chromite (Cr)

Aluminum-Goethite (Fe, Anatase (Ti) Albite (Si, Al)
Al)

Nordstrandite (Al) Hausmannite (Mn) Pyrite (Fe)

Woodruffite (Mn, Zn) Zircon (Si)
Crandallite (Ca, P) Feldspar (Al, Si)
 Bauxite Mineralogy
Al2O3
Gibbsite (hydrargillite) α-Al2O3.3H2O

Boehmite α- Al2O3.H2O
monohydrates Diaspore β- Al2O3.H2O

Tri-hydrate Sources
Gibbsite, Bayerite, norstrandite Al-Si-clays (kaolinite)
aluminian goethite
Types of bauxite Phosphate minerals:
Al3(PO4)2(OH)3.5H2O
– Gibbsitic bxt: < 2% boehmite
– Boehmitic bxt: > 5% boehmite Crandallite:
CaAl3(PO4)2(OH)5•(H2O)
– Mixed bxt: 2 – 5% boehmite
Double digestion & Sweetening processes
 Comparison of Alumina Minerals
Parameter Gibbsite Boehmite Diaspore
% Al2O3 65.4 85 85

Crystal System Monoclinic Orthorhombic Orthorhombic

Mohs Hardness 2.5-3.5 3.5-4.0 6.5-7.0

Dehydration Temperature,
150 350 450
°C

Product of dehydration χ-Al2O3 γ-Al2O3 α-Al2O3

Density, g/cm3 2.42 3.01 3.44

Solubility in 100 g/L NaOH Virtually

128 54
at 125 °C, g/L Al2O3 insoluble

(Chin, 1994; Sory et al., 2010)

 Silica – SiO2
Reactive SiO2 Un-reactive SiO2
 Kaolinite, halloysite  Mainly quartz

 Al2O3. 2SiO2.2H2O  Very compact structure

 Dissolves at 140oC  Significant inter-bonding

 Becomes supersaturated  Rarely dissolves at 140oC

 Co-precipitates with Al2O3  50% quartz dissolves at 240o

SiO2 Removal
Pre-desilication – to form Bayer sodalite
Process causes loss of Al2O3 & NaOH to mud
Bauxite with >7% SiO2 – often uneconomic to process
 Iron-bearing Minerals
 Al-goethite – ccp system of Hematite a-Fe2O3
Fe in ½ oh holes
Goethite a-FeOOH
 Isomorphous substn. of Al in
up to 30% of Fe sites Magnetite Fe3O4

Goethite causes: Siderite FeCO3

- poor settling & filtration Ilmenite FeTiO3
- precipitation of Bayerite
in mud circuit Al losses

Goethite to Haematite Transformation

Ca2+ + Cl- (SO42-) - 240oC

Goethite haematite
Ca2+ + Mn2+ (Fe2+)
Hematitic Jamaican Bauxite
Goethitic Jamaican Bauxite
 Goethite

Hematite
 Iron-bearing Minerals cont’d
Goethite to Haematite Transformation
– Roast bauxite at 500 oC
– No transformation leads to high capital cost

– Siderite: carbonation requiring causticization

Titanium
Anatase & rutile
Contaminates Al2O3
Forms CaTiO3 scale
May be used as a ‘tie element’ in low temp process
 Phosphorus
Pseudo-wavelite – dissolves readily in NaOH

Depletes NaOH in liquor:

P2O5 + NaOH Na3PO4 + 3H2O

P2O5 forms precipitate with CaO:

3CaO + P2O5 Ca3(PO4)2

Use of CaCO3 leads to NaOH loss:

2Na3PO4 + 3CaCO3 3Na2CO3 + Ca3(PO4)2

2Na3PO4 + 3CaO + 3H2O 6NaOH + Ca3(PO4)2

 Calcium
CaCO3 – major impurity

Causes liquor carbonation:

CaCO3 + 2NaOH Na2CO3

Contaminates Al2O3 product

Uses of CaO
SiO2 & P2O5 control
Liquor causticization
Goethite to haematite transformation
pre-coat filter cloths
increase liquor stability
 Zinc-bearing Minerals
Woodruffe – main contaminant
17% dissolves at 140 oC

Removal

NaS + Zn2+ ZnS

NaHS Zn2+ ZnS

Blow off liquor usually treated

 Organic Matter
0.1 – 0.6% of bauxite
Constituent of additives & flocculants
dissolves  Na2C2O4 & Na2CO3
Organics:
Influence Al2O3 yield & quality
Causes colouring of liquor and products
Causes frothing of liquor
Leads to unpleasant odours (VOC’s)
Form by-products that must be removed from the
process

Oxalate:
 toxic by-product; contaminates fine seed
 Adversely affects precipitation
 Major organic breakdown product
Mineralogical Composition of Some Bauxites
Al2O3 Ghana Aus Greece S. Man
Gibbsite 37.9 45.0 42.3
Boehmite 2 7.8 17.2 3.1
Other 2.3 4.2 43.8 1.6

Fe2O3
Haematite 15.3 6.0 18.5 15.1
Goethite 10.2 1.0 2.5 4.2
H/G 1.5 6.0 7.4 3.6

SiO2
Kaolinite 1.8 4.0 4.5 1.6
Quartz 0.7 1.0 0.1 0.5

TiO2
Rutile 0.4 0.4 1.7 0.5
Anatase 2.2 2.1 0.9 2.2
 Mineralogical Composition of Some Bauxites
Al2O3 Trelawny S. Man. St. Cath St. Ann
Gibbsite 30.2 36.6 39.9 44.6
Boehmite 12.7 8.0 6.1 1.7
Other 1.0 3.9 3.8 0.8

Fe2O3
Haematite 0.2 12.2 11.5 3.8
Goethite 20.8 1.0 2.5 15.8
H/G 0.01 1.7 1.8 0.24

SiO2 4.9 4.6 4.4 0.9

Most ideal for Low Temp processing?

Ideal for High Temp processing?
Problematic settling in mud circuit?
Large soda loss to DSP?
 Lecture Review
 Carefully consider the mineralogical characteristics
of the bauxites on the previous slide. Outline
preferred options for processing each ore and
discuss likely challenges that may be encountered
during processing. How could some of these
challenges be adequately dealt with?