Scribd Logo
Upload

Welcome to Scribd!

  • 1K views

    Brown Clinker

    Uploaded by

    Tamer Fathy
    Brown clinker produced at the Sötenich cement plant was causing brown cement and concrete surfaces, hurting competitiveness in pre-cast markets where color is important. Studies found brown clinker cores were caused by iron diffusing into the cores during rapid cooling in the kiln, bleaching the dark color of the clinker mineral C4AF. Recommendations included improvements to the burner to lengthen cooling times, use finer fuels and raw materials, and sort clinker by color. A new burner implemented in 2003 aimed to address the issues.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    Brown Clinker

    Uploaded by

    Tamer Fathy
    1K views21 pages
    Brown clinker produced at the Sötenich cement plant was causing brown cement and concrete surfaces, hurting competitiveness in pre-cast markets where color is important. Studies found brown clinker cores were caused by iron diffusing into the cores during rapid cooling in the kiln, bleaching the dark color of the clinker mineral C4AF. Recommendations included improvements to the burner to lengthen cooling times, use finer fuels and raw materials, and sort clinker by color. A new burner implemented in 2003 aimed to address the issues.

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Brown clinker produced at the Sötenich cement plant was causing brown cement and concrete surfaces, hurting competitiveness in pre-cast markets where color is important. Studies found brown clinker cores were caused by iron diffusing into the cores during rapid cooling in the kiln, bleaching the dark color of the clinker mineral C4AF. Recommendations included improvements to the burner to lengthen cooling times, use finer fuels and raw materials, and sort clinker by color. A new burner implemented in 2003 aimed to address the issues.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    1K views21 pages

    Brown Clinker

    Uploaded by

    Tamer Fathy
    Brown clinker produced at the Sötenich cement plant was causing brown cement and concrete surfaces, hurting competitiveness in pre-cast markets where color is important. Studies found brown clinker cores were caused by iron diffusing into the cores during rapid cooling in the kiln, bleaching the dark color of the clinker mineral C4AF. Recommendations included improvements to the burner to lengthen cooling times, use finer fuels and raw materials, and sort clinker by color. A new burner implemented in 2003 aimed to address the issues.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 21

    Brown clinker

    Brown cement
    Brown concrete
    Gerold Schnedl / Ingo Leth
    CTEC Quality Days 2003

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    The problem:
    Brown concrete
    G. Schnedl

    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    The reason: Brown clinker

    G. Schnedl

    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Situation

    Stenich plant:
    Brown cored clinker caused brown cement
    and brownish concrete surfaces
    Market focus: pre-cast cement
    Colour of cement / concrete important
    Cement less competitive
    Problems with brown cored clinker is not new
    (since years, but increased in 2002)
    but does not always appear
    Sometimes problems with brown stainings
    (Fe2+)
    Distinguish between:
    Fuels:
    Colour of cement
    Lignite, presently animal meal
    Brown stainings due to Fe2+
    Old burner, old grate cooler

    G. Schnedl

    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Study: Find levers to get black cores


    and grey cement

    Several industrial tests: Not successful

    September 2002: Start of systematic clinker sampling

    G. Schnedl

    Fuels, kiln conditions, clinker chemistry, granulometry

    Study in CTEC-Lab

    Higher amount of animal meal causes higher amount of Fe2+


    Brown clinker cores even without animal meal

    Literature study, microscopy, process data, lab burned


    clinker granules

    2003: Investment in new burner

    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Summary of findings
    Literature

    What causes dark / light clinker ?

    G. Schnedl

    C4AF is the only dark component in clinker


    Incorporation of Mg leads to dark C4AF - changes lattice
    parameters semi conductive properties leads to dark
    colour
    This electrical properties can be disturbed by even small
    amounts of other ions. e.g. Fe2+ Mn2+ , Ti4+ or Si4+
    Incorporation only when C4AF crystallizes: > 1250 C

    Colour depending on condition in sinter zone and


    pre-cooling condition (crystallisation) in kiln
    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    What bleaches C4AF in brown cores?

    Fe2+ seems to be the main reason in Stenich but:

    No Fe2+ in clinker after cooler does not necessarily mean


    that no Fe2+ in liquid phase in sinter zone

    Fe2+normally re-oxidised after sinter zone


    but needs time and oxygen

    Fe2+ appears not only due to reducing conditions:

    G. Schnedl

    Fe2+, Mn2+, Ti, Si in clinker cores: no significant differences


    detectable, but:

    a) reducing atmosphere or flame touching the lining


    b) fuel in clinker (too coarse material solid fuels..)
    c) thermal dissociation of Fe3+ in hot sintering zone
    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    What bleaches C4AF in brown cores?

    G. Schnedl

    Experience of plants:
    The core is brown and never the surface
    Bigger clinker granules have more often brown cores
    More often when kiln is operated at full capacity
    Hypothesis, resulting from literature study:
    Brown clinker cores seems to be caused by an diffusion effect:
    Balance of crystallisation speed of C4AF and re-oxidation of
    Fe2+
    Cooling speed > 1250 C (pre-cooling in kiln)
    O2 content in atmosphere / flame
    Porosity of clinker
    Liquid phase content
    Even when only very few FeO is detectable < 0,04 %) meaning that
    the not incorporated FeO oxidised afterwards
    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Confirmation of hypothesis
    Plant and lab tests

    Analysis of plant clinker samples and process data

    Extensive microscopic investigation in CTEC-Lab


    Lab burned clinker with Stenich raw material

    G. Schnedl

    Fuel mix / fuel rates


    burner positions

    Different cooling conditions over and below 1250 C


    Comparison with other raw meals
    Impact of atmosphere
    Impact of Manganese (Stenich: 0,2 % MnO in clinker)

    Feb 03

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Analysis of plant clinker samples

    brightness L* clinker meal

    Influence on animal meal on clinker colour


    68,00
    67,00
    66,00
    65,00
    64,00
    63,00
    62,00
    61,00
    60,00
    59,00

    No significant
    impact of animal
    meal on colour, but
    on FeO content
    0

    0,2

    0,4

    0,6

    0,8

    1,2

    tons / hour animal meal


    G. Schnedl

    Feb 03

    1
    0

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Analysis of plant clinker samples


    Brightness vs fineness
    400

    fineness k-value

    350
    300
    250

    (fineness)
    Coarse k-value
    clinker
    has
    brighter (browner)
    cores

    200
    150
    100
    58

    60

    62

    64

    66

    68

    Brightness L*
    G. Schnedl

    Feb 03

    1
    1

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Analysis of plant clinker samples


    Brightness (L*) vs Literweight
    1,70
    1,60

    literweight

    1,50
    1,40

    fraction 11,2-16 mm
    fraction 4-8 mm

    1,30
    1,20
    1,10
    1,00
    55,00

    60,00

    65,00

    Dense clinker
    granules (higher
    liter weight) have
    brighter
    cores
    70,00

    Brightness L*
    G. Schnedl

    Feb 03

    1
    2

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Microscopic examination

    G. Schnedl

    Fast cooling
    Partly reducing conditions
    No difference between brown and black cores
    High amounts of Alkali Aluminate
    Fast stiffening

    Feb 03

    1
    3

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Lab clinker tests

    G. Schnedl

    Feb 03

    1
    4

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Different cooling conditions

    G. Schnedl

    Feb 03

    1
    5

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Lab tests to check cooling conditions


    Check of different cooling rates > 1250 C in lab furnace

    a1

    G. Schnedl

    a2

    a3

    Feb 03

    1
    6

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Comparison of different conditions


    CIZ clinker
    Reference

    5 % MgO

    1 % MnO

    5 % MgO
    +1 % MnO

    Slow
    cooled

    quick
    cooled

    G. Schnedl

    Feb 03

    1
    7

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Results of process data an lab test study:

    Brown cores appear, even only very little FeO is


    detectable, nevertheless FeO is the cause
    Microscopy investigation confirms lab burning tests

    G. Schnedl

    Partly reducing conditions due to coarse fuel (lignite +


    animal meal) + divergent flame + sometimes thermal
    overheating
    Too rapid cooling: No pre-cooling zone in kiln caused by
    burner position
    Rather coarse raw mix causes overheating

    High Manganese content might boost the effect


    Coarse clinker granules favour brown cores due to
    oxygen diffusion barrier into the core
    Feb 03

    1
    8

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Recommendations

    Shorter flame shorter sinter zone

    Convergent flame not touching the clinker

    G. Schnedl

    Detrimental to clinker reactivity

    Finer fuels

    With old burner not possible

    Move burner into the kiln in order to lengthen cooling zone

    With old burner not possible

    No coal mill in Stenich

    Finer raw mix decrease coarse Quartz content (raw mill


    improvement)
    Increase SO3 in clinker in order to improve burnability and
    produce smaller clinker granules (+ increase workability)
    Feb 03

    1
    9

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Industrialisation: A new burner for Stenich

    Not only due to brown cores,


    also to increase waste fuel
    rate
    Start: 21.05.2003
    Shorter, convergent flame
    Controllable

    G. Schnedl

    Feb 03

    2
    0

    Brown clinker Stenich


    CENTRE TECHNIQUE EUROPE CENTRALE

    Other plant actions

    Manual estimation of clinker colour

    G. Schnedl

    Only black clinker for precast cement


    Target: Implement automatic colour measurement of press
    tablets in auto-lab result triggers separation of clinker

    Implement FeO quick test

    separation

    Separate clinker
    Change fuel mix (reduce
    animal meal)

    Result: No claims in 2003


    Feb 03

    2
    1

    You might also like