PMO KOMEX Sp.z o.o.

, Krakow, Poland
(A 100% Subsidiary of ArcelorMittal Poland S.A)

DOLOMITE CLINKER PRODUCTION

FOR MODERN STEELMAKING
Czesław Golawski,
Michal L.Sulkowski,

11th BIENNAL WORLDWIDE CONGRESS

13-16 October, 2009
Pestana Bahia Hotel-Salvator-Brasil
 Production Process
• High-temperature sintering of mixture of raw
dolomites at the temperature up to 1900oC

• Sintered dolomite is ground in cone crushers and

then the mass is prepared by the hot method with
the addition of pitch-based polymer binder.

• Hot mass obtained is moulded into bricks under

high pressure on the LAEIS presses.

• Heating in 300 oC in neutral atmosphere

• Packing in double layer foil

 Chemical Reaction
of
Raw Dolomite to Dolomite Clinker

CaCO3.MgCO3  CaCO3 MgO  CaO.MgO

dolomite 650oC 850oC dolime

CaO.MgO (dv=1,4 g/cm3)  CaO.MgO (dv=3,15 g/cm3)

dolime sintering in rotary kiln dead burned dolomite
Rotary Kiln for Dolomite Clinker Production
 Increasing of Hydration Resistance
• through improving the degree of clinker sintering, tempering of products after moulding
and packing together with protecting the products with thermo-shrinkable foil,

Binding System Development

• continuous improving of the quality of polymer binder for ecological low PAH
and optimization of hot mass preparation

• working out a conditioning at the temperature 300oC resulted in improving the

working conditions and facilitated the heating up process after lining the
products in vessel.

Composition Development
• working out technological alternatives of combined dolomite-magnesia products along with
replacing the fine-grained fast hydrating dolomite clinker fraction with magnesia clinker

• working out new technological solutions in the semi-technical trials of two-step sintering
dolomite clinker.
 Raw Material
Triassic dolomites DK, DWH and dewon dolomite from Silesia-
Krakow region of Siewierz deposits are used for the production
of dolomite clinker.

Dolomite
stone SiO2 Al2O3 Fe2O3 MgO Porosity %

DWH-Triass 0,9 0,36 2,07 18,63 7,84

DK-Triass 0,37 0,26 1,02 19,38 7,76

Dewon
0,16-0,6 0,17-0,54 0,1-0,34 19,63-22,19 1,4-3,2
dolomite
Thermal Analysis
Dolomite DWH
of Raw Dolomite

Higher mass loss (48,37%

at 1000oC of dolomite DK
quality, is a consequence
Dolomite DK of higher chemical purity
 Dolomite Clinker from Rotary Kiln
Mictrostructure
Mixed crystal, magn. 2500x Closed pores magn. 600x
 Dolomite Clinker Application
• After cooling, the dolomite clinker is crushed in
cone crushers to save undamaged glazed aggregate
surface directly used in moulding composition.

• Melted polymer binder enables the moulding of

products, but also to protect the dolomite grains
against rapid hydration and to retain the binding
carbon residue after coking which reduces the
corrosion process by metallurgical slags.

• Main application of dolomite products is steel ladles

lining where the products made by PMO ‘Komex’
have a very good performance.
 Influence of Burner Type on the Quality
of Dolomite Clinker.
In June 2008 the burner fired by coal pitch in the high-
temperature rotary kiln was replaced with a burner fired with
gas. Although the major purpose of the project was to reduce
the energy consumption, after a short period of commissioning
of the kiln a significant improvement of clinker quality was also
achieved and mostly the homogeneity was increased.

Type of burner Oil burner Gas burner

Total porosity % 3.30 ±1,4 1.35±0,9

Bulk density g/cm3 3.175± 0,4 3.23± 0,2

Change of temperature profile in zones improved

homogenisation of input before sintering.
 Trial of Two-steps Dolomite Clinker Production
The decarbonization of dolomite was carried out at the temperature of 1100oC.

Properties of dolomite after decarbonization

Type of dolomite DK DWH
Total porosity % 57.5 58.3

Bulk density g/cm3 1.47 1.44

Specific surface area 1.33 1.51

BET, m2/g

Decarbonates have a high total porosity and a low bulk density but crystal size of
DK> DWH. Total porosity of raw dolomites of DK and DWH is up to 10% of
decarbonization generate very big increase of porosity.

Tests of densification of the decarbonate of DK quality v. pressure of moulding

carried out in the range 120 MPa to 320 MPa. Increase of moulding pressure was
linear and resulted in total porosity change from 45,9% to 35,9%.
 Trial of Two-steps Dolomite Clinker Production

Briquettes moulded with high pressure from decarbonates were burnt at the
maximum temperature of 1600oC

Properties of dolomite clinkers

Type of dololmite Rotary kiln one DK DWH

step product
Total porosity % 2.2 1.2 2.2
Bulk density g/cm3 3.2009 3.3433 3.2485
Density g/cm3 /He/ 3.2703 3.3425 3.3226

Clinkers obtained from DK and DWH qualities, (X-Ray) the main phases are
crystalline calcium oxide, periclase, small quantities of calcium hydroxide
and calcium aluminates: C3A and C12A7.
In the second sintering step coarse-crystalline DK quality dolomite (lower
content of iron compounds) does not sinter worse than dolomite DWH (higher
iron content) but even better.
 Microstructure of the Two-Step Sintering Trials
The pores are mainly of the closed type, which have a positive effect
on the hydration resistance and also the reduced infiltration of slag
was observed

Decarbonized dolomite DK Second step sintered dolomite DK

Investigation in scanning microscope NOVA NANOSEM 200 (FEI), 2500x

 Two Step Sintering of Dewon Dolomite
Dr inż. Zygmunt Piotrowski research on two step sintering of Siewierz deposit
Dewon dolomite – calcined samples, ground and pressed sample for sintering

Type of dolomite DK SIEWIERZ

TRIAS DEWON
crystal size 100-150 um crystal size 750-900 um

Sintering effect % of initial surface % of initial surface

two steps 37,3 35,6

one step 53,3 81,2

10 Tons of Dewon Dolomite stone calcined in 1100 oC, ground to 0,6 mm

briqueting without binder into 50x35mm with pressure 520 MPa to prosity 5,8 %
density 2,98 g/cm3. Briquets fired in 1700 oC in rotary kiln.

Clinker properties: porosity 2,4-2,7 %, density 3,2-3,5 g/cm3. Applied for pitch
bonded bricks- wear rate was 30-35% better than fine crystals triasic dolomite.
Properties of the Dolomite Refractories
Dolomite refractories of 40% MgO are currently used in linings of steel ladles –
their performance in a number of steel plants is very good:

Grade 42D7 42D9 42D11 4RD9

CCS 40 30 25 50
MPa
Porosity 4 3 2 3
%
Density 2,95 2,95 2,95 2,95
g/cm3
Carbon 7 9 11 9
content %
Binder type carbon polymer resin
The carbon additive (7-11%) reduces the iron oxides lowering the chemical
corrosion and by its low wetability limits metal penetration into the products

Further improvement of the quality of dolomite clinker could be expected

when introducing the two-step method of sintering. That, would require
substantial investment expenditure in the form of devices for
decarbonization, making pellets and the RCE shaft kiln.
The trials of fusing dolomite have also brought interesting results.
 Steel Ladle –Dolomite Lining
LCC
Manesite Bauxite-Spinel
Ramming Mix

M90, HA55, 40D11

MCr90
50D11
M90, HA55,
60D11
MCr90

Dolomite
Ramming
Mix 40D

40D7
M90, HA55,
MCr90
MSP5-DK

M90, HA55, MCr90

LCC
Bauxite-Spinel
MCC, Bauxite-Corundum
 Conclusion - Dolomite v. Magnesia
1. Increased of costs of purchase of good quality
magnesia clinker.

2. Dolomite raw material is more available and

cheaper than the magnesia raw material.

3. In many applications dolomite products can

successfully compete with magnesia products
for higher resistance in special metallurgical
treatment the silica-rich slags application.
Free CaO reacts with low-basic slag, in fused
slag calcium silicates are formed on brick
surface, thus reducing the corrosion process
 Conclusion - Dolomite v. Magnesia
4. Combination CaO-C is more stable above
1600ºC comparing to MgO-C combination,
(carbothermical reaction ).

5. The production of dolomite products is

important in Poland where there is a
shortage of good quality raw material for the
production of magnesia products, and on the
other hand there are large deposits of good
quality dolomite and so there are the
conditions to produce this type of refractory
products.
 THANK YOU
FOR YOUR ATTENTION