New developments in refractories for the cement industry

G&W Training Program: Refractories in the Portland Cement Industry

Cairo, June 9-14, 2007
Lars Vieten, REFRATECHNIK Cement GmbH
Product development by REFRATECHNIK

• AF – Alternative Fuels • AR – Alkali Resistant

refractory concrete
ALMAG® AF
TOPMAG® AF • Gas-tight lining concept
REFRAMAG® AF
TOPMAG® A1 basic

• AR – Alkali Resistant

KRONAL® 50 AR
KRONAL® 60 AR high
KRONAL® 63 AR alumina
Main reason for increasing wear on the refractory lining

• AFR

Alternative Fuels
and Raw materials
Reasons for the use of alternative fuels and raw materials

Economical

Saving of precious
resources

Reduction of CO2
emissions
(Kyoto-protocol)

Step towards sustainable

cement industry
Examples of alternative fuels and
alternative raw materials Alternative Fuels:
tires, plastics
household waste
waste oil, solvents
sewage sludge
animal fat, bone meal
etc.
Alternative raw materials:
contaminated soil
fullers earth
foundry sand
fly ash
glass
gypsum
etc.
Examples for economical and environmental benefits
in case of usage of dry sewage sludge
(example Switzerland)

• 1 mt of dry sewage sludge replaces:

0,3 mt hard coal 0,6 mt raw material

• 1 mt of sewage sludge reduces CO2-emission by 0,8 mt

Disadvantages of replacement of conventional
fuels and raw materials by alternatives

• Inhomogeneous burning • Enrichment of volatile compounds

conditions resulting in: in the kiln atmosphere resulting in:

- changing coating conditions - operational problems

- formation of coating rings) - physical and/or chemical reaction with
- infiltration of clinker into the the refractory lining
refractory lining - kiln shell corrosion
- local thermal overloading - alkali infiltration
- redox changes - alkali spalling

reduced lifetime of the refractory lining

Coating variation observed during the usage of different fuels

Regular fuel: oil, gas

Regular fuel: coal, oil

Mix of regular fuel and

alternative fuel
Circulation phenomena in cement kilns
Infiltration in the basic zone
of cement rotary kilns
Main volatile elements or compounds
(heavy metals not considered)

Sulphur
SO2, SO3, S2-

Potassium
K2O

Sodium
Na2O

Chlorine
Cl2, Cl-
Sources of alkali metals

Raw material
Na,K as interlayer caption in clay minerals and feldspar
potassium feldspars (Na,K)Si3O8
plagioclase (Na,Ca) (Si,Al) Al2Si2O8

Additives (ashes, slags, bentonite, etc.)

Sources of chlorine

Raw material, sea water

Plastics »PVC«
20 % of world-wide production of »plastics«
CH2=CHCl 30% Cl (tolerance level approx. 2-3%)
Bitum. Coal 0,01 – 0,3% Cl
Lignite 0,01 – 0,13% Cl
Sources of sulphur

Raw material: FeS2, PbS, ZnS, CaSO4, CaSO4 H2O

Fuel oil 0,2 – 2,5% SO3

Crude oil 1 – 5% SO3
Bitum. coal 0,1 – 12% SO3
Lignite 0,2 – 15 % SO3
Output of circulating elements

• with clinker as compounds

K2SO4, K3Na(SO4), Na2SO4, Ca2K2(SO4)3
• dissolved / solid solution in clinker minerals
K: belite, aluminate
Na: aluminate
SO3 belite

• with refractory material

Impact of volatile elements on kiln operation

Process Refractory lining

• build-ups
• ring formation
• encrustation
• clogging
• unstable burning and
• coating conditions
• (heat transfer)
• weakening and destruction
of the refractory lining
• corrosion of steel construction and
• refractory anchoring system
• alteration of heat transfer
• lifetime reduction
Alkali attack on basic bricks

• Volatile elements infiltrate the bricks and condense

as salt compounds

• The condensation densifies the brick matrix by

filling of pores

• The mineralogical and physical properties are

impaired

• Crystallisation pressure builds up

• This typically results in formation of cracks and

spalling along the salt infiltrated layers occurs
Alkali attack on basic bricks

Salt accumulations in distinct brick

horizons cause crack formation.

The lifetime of the lining is reduced

due to spalling.

Spalling typically occurs:

a) during heating up
after a shut down
b) when mechanical loads
are acting upon the lining
Alkali spalling in basic lining
Infiltration and destruction by sulfate salts

• Presence of excess
sulphur in the kiln
atmosphere
• Formation of
oldhamite (CaS), K2S3,
KFeS2 under
reducing atmosphere
• If oxidizing atmosphere is
dominating again,
sulphate salts are formed
and the brick structure is
destroyed
• Typical H2S smell
during shut-down
Infiltration by other volatile compounds

PbS-infiltration due to
burning of i.e. batteries or
burning of contaminated
material such as:

quartz sands from

sandblasting,
etc.
Alkali attack on alumina bricks

Formation of new minerals

combined with overheating
Wear reasons based on a recent survey

> 60%
New shaped products for thermo-chemically stressed kilns

REFRAMAG® AF Alternative Fuels

TOPMAG® AF Alternative Fuels

Basic bricks
ALMAG® AF Alternative Fuels

TOPMAG® A1 Alternative Fuels

KRONAL® 50 AR Akali Resistant

KRONAL® 60 AR Akali Resistant High alumina bricks

KRONAL® 63 AR Akali Resistant

AF basic refractories
AR alumina based refractories
Product development by REFRATECHNIK

• AF – Alternative Fuels • AR – Alkali Resistant

ALMAG® AF refractory concrete
TOPMAG® AF
REFRAMAG® AF • Gas-tight lining concept
TOPMAG® A1

• AR – Alkali Resistant
KRONAL® 50 AR
KRONAL® 60 AR
KRONAL® 63 AR
Main product line – basic bricks (main component MgO)

Magnesia Magnesia Magnesia Magnesia

MA-Spinel Chromite FA-Spinel (Hercynite) Zirconia

MAGPURE® 93 PERILEX® 80 FERROMAG® 90 MAGNUM®

REFRAMAG® 85 PERILEX® 83 FERROMAG® F1

ALMAG® 85 PERILEX® 80 S

ALMAG® A1 PERILEX® 83 S

REFRAMAG® AF Magnesia
Chrome & spinel free
TOPMAG® AF

ALMAG® AF MAGPURE® O1
Innovations
TOPMAG® A1 Recent products
Constant further development of main basic products

ALMAG® 85 ALMAG® A1 REFRAMAG® 85

magnesia spinel bricks on

Alternative Fuels basis of ALMAG technology

ALMAG® AF TOPMAG® AF REFRAMAG® AF

high temperature resistant highly elastified

MAGNUM® TOPMAG® A1
Influence of infiltration on elasticity of refractory bricks

150
modulus of
75 GPa
elasticity
40 GPa
in GPa
20 GPa
100

50

0
0 20 40 60
infiltrate saturation / %
Correlation between modulus of elasticity and porosity
– Standard bricks
45

Risk of spalling
Modulus of Elasticity (GPa)

30

15
Area of safe operation
13 15 17 19

Porosity (%)
Goals for REFRATECHNIK’s R&D Department

• Increase resistance to penetration

• Reduce permeability

• Maintain structural elasticity (thermal shock resistance)

• Increase strength (cold crushing strength + modulus of rupture)

Pore structure of magnesia spinel brick grades

standard magnesia spinel brick TOPMAG® AF

Comparison between standard magnesia spinel bricks and AF products

150
Standarsized Properties [%]

100

50

0
Bulk Density Porosity Permeability CCS MOR Modulus of
Elasticity

AF-Products Standard Products

Correlation between modulus of elasticity and porosity
– Standard bricks and AF products
45

Risk of spalling
Modulus of Elasticity (GPa)

30

AF products

Area of safe operation

15
13 15 17 19

Porosity (%)
Performance example ALMAG® AF at Lafarge Karsdorf, Germany
KHD 4.6 x 68m, preheater kiln

• first installation of a 220mm brick took place in August 2000

• typical lifetime of upper transition zone (UTZ) was previously 18 months
• residual thickness after 15 months: approx. 200 mm
• residual thickness after 18 months: approx. 190 mm
• adjacent lining of conventional bricks removed after 18 months
• current lifetime > 24 months
• ALMAG® AF was reordered and installed into LTZ as well
ALMAG® AF after 15 months
– UTZ – chemically loaded kiln
ALMAG® AF after 15 months
– UTZ – chemically loaded kiln
Bricks are partially densified

No significant formation of
cracks

No embrittlement of brick
matrix

No chemical destruction of
bonding phases
Performance example ALMAG® AF at Readymix Beckum Plant, Germany
KHD 5.3 x 80m, 4-stage preheater kiln, 3,300 t/d

• first installation of ALMAG® AF at Beckum in November 2001

• typical lifetime of lower transition zone (LTZ) was previously 5 to 8 months
• residual thickness after 12 months: approx. 180 mm
• lifetime 12 to 14 months
• ALMAG® AF was reordered for installation in LTZ and UTZ
ALMAG® AF

used at:
Lower Transition Zone
(K.P. 8m)
after 12 months
operation
remaining thickness
180mm
ALMAG® AF

Structure cut of
ALMAG® AF sample:
remaining thickness
180 mm

severe salt infiltration

(Arcanite K2SO4) in
brick head

no structual spalling
Performance example ALMAG® AF at Portland Zementwerk Wittekind
Miag-WT 4.6 x 70m, 5-stage preheater kiln

• first installation at Wittekind in March 2001

• typical lifetime of lower transition zone (LTZ) was previously 3-4 months
• residual thickness after 9 months: approx. 170 mm
• lifetime > 14 months
• ALMAG® AF was reordered for installation into LTZ
References – ALMAG® AF, TOPMAG® AF, REFRAMAG® AF
ALMAG® AF TOPMAG® AF REFRAMAG® AF TOPMAG® A1

Superior resistance against alkali infiltration and

wear by alkalis

Improved resistance against infiltration and

corrosion by cement clinker phases

Combination of high strength with high elasticity counteracting

any loosening of the structure by infiltration

Thermal shock resistance comes up to the excellent properties of

ALMAG® 85
Fields of application of ALMAG® AF, TOPMAG® AF, REFRAMAG® AF
and TOPMAG® A1

Typical fields of application • Thermochemically stressed

transition- and burning zones

• Alkali salt infiltration,

embrittlement, spalling

• Infiltration by liquid and

gaseous phases – i.e. PbS,
etc.

• Infiltration by clinker phases,

spinel corrosion
Product development by REFRATECHNIK

• AF – Alternative Fuels • AR – Alkali Resistant

ALMAG® AF refractory concrete
TOPMAG® AF
REFRAMAG® AF • Gas-tight lining concept
TOPMAG® A1

• AR – Alkali Resistant
KRONAL® 50 AR
KRONAL® 60 AR
KRONAL® 63 AR
Main product line – fireclay and high alumina bricks

KRONEX® KRONAL® REFRALUSIT® REFRATHERM®

25 Special 50 AR 61 150
30 Fireclay Special High Al. Andalusite, Bauxite Lightweight
40 Fireclay, insulating brick,
50 Special High SiC 63 22 - 26% Al2O3
Al. Fireclay Andalusite
60 AR
60 Bauxite, Andalusite,
Fireclay SiC

70 Bauxite 63 AR Innovations
Andalusite, Recent products
85 Diaspore SiC
87 Gibbsite AR - Highly Alkali Resistant
Constant further development of main high alumina bricks

KRONEX® 50

KRONEX®
standard 50% Al2O3 brick

KRONAL® 50 AR Alkali Resistance

KRONEX® / REFRALUSIT®

Alkali Resistance
high wear by abrasion and thermal shock in outlet zone

KRONAL® 63 AR KRONAL® 60 AR
Alkali attack on alumina bricks and concretes

unaffected microstructure destruction of grains Formation of new

minerals i.e. feldspar,
leucite, calsilite

Volume expansion
of up to 30% causes
alkali-bursting
Silicon carbide technology

• SiO2 + 3C SiC + 2CO

• Extreme hardness
• High refractoriness
• High thermal conductivity
• Very high hot abrasion resistance
• Excellent thermal shock behaviour
• Formation of protecting layer of SiO2
• Ideal material for mechanically and
chemically loaded wear parts
Results of Development
K2CO3-crucible test according DIN 51069

brick with 50 % Al2O3 KRONAL® 50 AR

In-situ surface sealing mechanism
microstructure after alkali attack

dense layer

SiC

phase
transformation

brick with 50 % Al2O3 KRONAL® 50 AR

In-situ surface sealing mechanism
monolithic material containing SiC ( REFRA-SiC AR )

glassy surface
Results of Development
Properties of classical high alumina bricks and a new alkali resistant high alumina brick grade

High alumina brick KRONAL® 50 AR

containing
50% Al2O3
Raw material high alumina high alumina
special fireclay special fireclay,
silicon carbide
Bulk density (g/cm3) 2.30 - 2.50 2.30-2.45
Porosity (%) 14 – 18 13-15
CCS (N/mm2) 60 70
Refractoriness
under load ta (°C) 1450 1450
te (°C) 1650 1700
Thermal conductivity W/(mK) 1.4 1.5
(at 1000 °C)
chem. composition
Al2O3 50 – 55 48 - 53
SiO2 40 – 45 37 - 42
Fe2O3 1.5 1.5
SiC - 3-6
Performance of KRONAL® 50 AR
Lining installed in a
security zone.

Lifetime of
conventional high
alumina bricks:
6-8 month

Current lifetime with

KRONAL® 50 AR:
21 months.

Still in use!
Performance example of KRONAL® 50 AR

Safety zone lined with

KRONAL® 50 AR

Photo taken after more

than one year of operation

... grooves are still visible !

Installation of KRONAL® 50 AR

Spalling of thin surface

layers resulting in an un-
even lining surface is
normal.
KRONAL 50 AR
Protecting layer will form
again on the exposed
surface.
KRONAL® 50 AR and KRONAL® 60 AR

High resistance against wear by alkalis

Typical properties of 50 % bricks are maintained or improved

Inert brick surface reduces formation of build-ups (cyclone, rings)

Improved abrasion resistance

Available in special shapes for installation in the rotary kiln as well as in

other aggregates
Fields of Application of KRONAL® 50 AR and KRONAL® 60 AR

Typical fields of application

Safety Zone
Preheater
Kiln Hood
Cooler

Anchor brick for alkali resistant

monolithic linings
Increased SiC content
use of small SiC amounts
3-6%
products with properties very close
to standard high alumina materials,
but with additionally high alkali
resistance
brick: KRONAL® 50 AR
concrete: REFRAMULLITE 63 LCC
use of higher SiC amounts
> 15 %
trouble shooters with high hot
abrasion-, alkali-, thermal shock and
thermal resistance for special kiln
zones
increased thermal conductivity has to
be respected
brick: KRONAL® 63 AR
concrete: REFRAMULLITE 63 LCC AR
REFRA-SiC AR
Results of Development
Properties of high alumina bricks and of a new brick grade containing 23 - 27 % SiC
High alumina brick KRONAL® 63 AR
containing
63 % Al2O3
Raw material basis andalusite andalusite
silicon carbide

Bulk density (g/cm3) 2.55 - 2.70 2.50-2.65

Porosity (%) 12 – 14 14-16
CCS (N/mm2) 70 55
Refractoriness
under load ta (°C) 1700 1550
te (°C) >1700 1700
Thermal conductivity W/(mK) 1.6 3.6
(at 1000 °C)
chem. composition
Al2O3 59 – 63 42-46
SiO2 33-37 26-30
Fe2O3 1.0 1.0
SiC - 23-27
Appearance of KRONAL® 63 AR

Typical colour of
KL 63 AR

Dark coloration
is normal
Installation of KRONAL® 63 AR – Dyckerhoff Beckum, Germany
FLS 5,5 x 90m

Kiln outlet section lined with

KRONAL® 63 AR
installed in 08/2001

Lining:
0.00m – 0.40m 75% Al2O3
75% 75% 0.40m – 2.40m KRONAL® 63 AR
KRONAL® 63 AR 2.40m – 4.60m 75% Al2O3
Performance of KRONAL® 63 AR – Dyckerhoff Beckum, Germany

Kiln outlet section lined with

KRONAL 63 AR
75% installed in 08/2001
Photo taken in 06/2002
Damaged and worn 75%- lining
KRONAL® 63 AR
Lining:
0,00m – 0,40m 75% Al2O3
0,40m – 2,40m KRONAL 63 AR
2,40m – 4,60m 75% Al2O3
Performance of KRONAL® 63 AR – Dyckerhoff Beckum, Germany

Kiln outlet section lined with

KRONAL® 63 AR
KRONAL® 63 AR installed in 08/2001

Photo taken in 06/2002

75%
Lining:
0.00m – 0.40m 75% Al2O3
0.40m – 2.40m KRONAL® 63 AR
2.40m – 4.60m 75% Al2O3
Installation of KRONAL® 63 AR – Readymix Rüdersdorf, Germany

Kiln hood under the

horizontal support for
the basic arch lining
AR concrete
Support brackets
protected with AR-
concrete

KRONAL® 63 AR
KRONAL® 63 AR

Extreme resistance against wear by alkalis due

to combination of andalusite matrix with approx. 25% SiC

Very high thermal shock resistance

Excellent resistance against abrasion

Increased thermal conductivity should be taken into consideration

Most suitable also for special applications, i.e. cam linings, dam rings, etc.
Fields of application of KRONAL® 63 AR

Typical fields of application

• Outlet zone (behind burner tip)

• Inlet zone of grate cooler
• Elbows of satellite cooler tubes
• Side walls in kiln hood
• Cooler curbs (kerbs)

• Special application in the

grate cooler and satellite cooler
tubes
Fields of application of „AF“ and „AR“ brick types

Safety Zone, Upper Transition Zone, Outlet Zone

Preheater Burning zone,
Lower Transition Zone

high alumina brick magnesia bauxite brick,

spinel brick magnesia
spinel brick

KRONAL® 50 AR ALMAG® AF KRONAL® 63 AR

KRONAL® 60 AR TOPMAG® AF ALMAG ® AF
REFRAMAG® AF TOPMAG® AF
TOPMAG® A1
Product development by REFRATECHNIK

• AF – Alternative Fuels • AR – Alkali Resistant

ALMAG® AF refractory concrete
TOPMAG® AF
REFRAMAG® AF • Gas-tight lining concept
TOPMAG® A1

• AR – Alkali Resistant
KRONAL® 50 AR
KRONAL® 60 AR
KRONAL® 63 AR
Modern Castable Lining Concept
Jetcast-, SIC-technology, low- and medium cement technology (LCC & MCC)

REFRALITE® 40 G 2-layer lining concept, 1250 °C

REFRALITE® 30 G 2-layer lining concept, 1150 °C
REFRACLAY 40 G Easy & fast installation technology
REFRACLAY 40 (raw meal duct)

REFRACLAY 40 LCC Premium grade product properties

REFRACLAY 40 LCG Easy & fast installation technology
REFRACLAY 40 JC Fast installation technology, 3 – 8 t/h

REFRACLAY 40 MCG AR Easy & fast installation technology

REFRACLAY 40 JC AR Premium grade product properties, 3 – 8 t/h

REFRACLAY 40 LCC AR Premium grade product properties

REFRAMULLITE 63 JC Premium grade product properties, 3 – 8 t/h

REFRAMULLITE 63 JC AR Premium grade product properties, 3 – 8 t/h

REFRA-SiC MCG AR Easy & fast installation technology

REFRA-SiC AR dense, low cement SiC-castable;

REFRA-SiC 50 AR very high alkali-, sulphate- and chloride-
resistance
Product development by REFRATECHNIK

• AF – Alternative Fuels • AR – Alkali Resistant

ALMAG® AF refractory concrete
TOPMAG® AF
REFRAMAG® AF • Gas-tight lining concept
TOPMAG® A1

• AR – Alkali Resistant
KRONAL® 50 AR
KRONAL® 60 AR
KRONAL® 63 AR
Conventional lining concept
• penetration through concrete
• penetration via expansion joints
• hot gas corrosion of anchors and
metallic supports
gas penetration

area of
expansion
hot gas
joint
corrosion

gas penetration
metallic
supports
REFRATECHNIK‘s AR lining – wall structure

AR lining concept
gas tight lining concept
REFRATECHNIK‘s AR lining concept
REFRATECHNIK’s AR-lining concept

• two layer lining REFRA-Block line

• insulating castable
• working layer in channels to
the steel shell

Preparation of channels
and insulating fields
Conclusion

1. New shaped refractories for thermo-chemically

loaded cement kilns

2. New monolithic refractories for thermo-chemically

loaded cement kilns

3. New engineering concepts: AR-lining

„gas-tight lining“