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    Bayer Process Chemistry: Dr. M. Coley

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    Toanique Headman
    1) Bauxite is the main ore of aluminum. It varies in appearance and is often found near limestone deposits, deposited by underground streams. 2) Bauxite is characterized using techniques like XRD, XRF, ICP, and LOI to determine its mineral composition and impurities. 3) The main minerals present are gibbsite, boehmite, hematite, and goethite. Impurities like silica,

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    Bayer Process Chemistry: Dr. M. Coley

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    Toanique Headman
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    1) Bauxite is the main ore of aluminum. It varies in appearance and is often found near limestone deposits, deposited by underground streams. 2) Bauxite is characterized using techniques like XRD, XRF, ICP, and LOI to determine its mineral composition and impurities. 3) The main minerals present are gibbsite, boehmite, hematite, and goethite. Impurities like silica,

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    Bauxite Lecture 4

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    1) Bauxite is the main ore of aluminum. It varies in appearance and is often found near limestone deposits, deposited by underground streams. 2) Bauxite is characterized using techniques like XRD, XRF, ICP, and LOI to determine its mineral composition and impurities. 3) The main minerals present are gibbsite, boehmite, hematite, and goethite. Impurities like silica,

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    Bayer Process Chemistry: Dr. M. Coley

    Uploaded by

    Toanique Headman
    1) Bauxite is the main ore of aluminum. It varies in appearance and is often found near limestone deposits, deposited by underground streams. 2) Bauxite is characterized using techniques like XRD, XRF, ICP, and LOI to determine its mineral composition and impurities. 3) The main minerals present are gibbsite, boehmite, hematite, and goethite. Impurities like silica,

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    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?

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