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