Refractory Materials

Refractory
CMC APAC, Fall 2014, Michael Kapphahn EPT-TT
CMC APAC Fall 2014, 2014-09-01 © 2014

Content
1. Refractory materials
 Introduction
 Alumina refractory
 Basic refractory
 Shaped and Unshaped
2. Rotary kiln bricklaying
 General design
 Installation methods
3. Static kiln part lining
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 2

Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 3

Some raw materials and their melting points
Melting points of common refractory materials
MgO 2840
ZrO2 2680
CaO 2580
oxides
Cr2O3 2275
Al2O3 2050
SiO2 1725
nonmetals carbides
WC 2870
SiC 2700
C 3550
B 2180
W 3410
Mo 2671
metals
Rh 1966
Pt 1772
0 500 1000 1500 2000 2500 3000 3500 4000

temperature / °C
CMC APAC Fall 2014, 2014-09-01 © 2014 4

Definition
Definition in standard:
Refractory, refractory product and refractory material are defined
according to ISO 836:2001 as follows:
“Non-metallic material or product (but not excluding those
containing a proportion of metal) whose chemical and physical
properties allow it to be used in a high temperature
environment“.
Source: www.pizzaofen.com
CMC APAC Fall 2014, 2014-09-01 © 2014 5

Refractories developed over the past 100 years
alumina
basic
Refratechnik Seminar 2012
CMC APAC Fall 2014, 2014-09-01 © 2014 6
Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 7

Alumina-Silica phase diagram
high-alumina products fireclay products The formation of the first

melt in the alumina-silica
system is at 1590°C.
Most of the impurities
(K2O, Na2O, CaO, MgO,
Fe2O3) will act as fluxes
and lower the melting
point considerably:
• to 1250°C with Fe2O3
• to 985 by K2O
Al2O3 SiO2
(Alumina) (Silica)
CMC APAC Fall 2014, 2014-09-01 © 2014 8

Alkali resistance vs. heat resistance
The refractoriness of alumina

bricks increases with the Al2O3
content.
The resistance to alkali attack
decreases with higher Al2O3
contents.
Al2O3 SiO2
(Alumina) (Silica)
High refractoriness and high alkali resistance compete in an alumina-silica

15 % apparent
brick. porosity
CMC APAC Fall 2014, 2014-09-01 © 2014 9

Alumina-silicate bricks
Products Proportion of major component
Acidic fireclay bricks 10% ≤ Al2O3 < 30% and SiO2 < 85%
Fireclay bricks 30 % ≤ Al2O3 < 45%
High-alumina bricks 2 45% ≤ Al2O3 < 56%
High-alumina bricks 1 Al2O3 ≥ 56%
The raw material for acidic fireclay and fireclay bricks are naturally
occurring clays such as Kaolinite and are thus limited in the Al2O3 content.
Because of the use of natural raw materials, the impurities play a crucial
role in their properties (formation of low melting phases).
High alumina products are based on various natural and synthetic raw
materials such as: i.e. sintered and fused corundum, sintered bauxite,
sintered and fused mullite, andalusite, sillimanite, kyanite, calcined
alumina.
CMC APAC Fall 2014, 2014-09-01 © 2014 10

Alumina-silicate bricks - Special applications
Silicon carbide (SiC)
• SiC is synthesized by the reaction of silica (quartz sand) and coke at
temperatures above 2’000°C:
 SiO2 + 3C = SiC + 2CO
• Silicon carbide is sensitive to i.e. air and water vapor at
temperatures above 900°C and oxidizes to SiO2 (where in
combination with alkalis it will form a protective layer):
 SiC + 2O2 → SiO2 + CO2
 SiC + 2 H2O → SiO2 + CH4
• Bricks with higher SiC contents (> 30%) should not be used in
cement kilns (high thermal conductivity & economic point).
without SiC
with SiC
Refractory Seminar 2013 © 2014 11
SiC addition
CMC APAC Fall 2014, 2014-09-01 © 2014 12

Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 13

Basic refractory
• For the lining of the rotary part of the kiln mainly basic bricks
are used.
• Basic refractories contain the main oxides: MgO & CaO.
• Modifiers used nowadays:
 Spinel, hercynite, galaxite, zirconia
• Environmental considerations and regulations concerning the
disposal of chrome containing refractories have led towards
the use of chrome-free alternatives.
• The basic bricks used in burning and transition zones have a
ceramic bonding which is achieved by burning the pressed raw
bricks at temperatures around 1’550-1’700°C.

Composition
80-95% Component A 5-20% Component B
Matrix Modifier/elastifier
MgO Dolomite
(NATURAL) Chromite Spinel Zirconia
(NATURAL) (SYNTHETIC)
NATURAL SYNTHETIC
PREFABRICATED IN SITU
Electrofused During Burning Process: CaO•ZrO2
Sintered •Corundum (SYNTHETIC)
•Tabular Alumina
•Calcined Alumina
ZrO2
(NATURAL)
MA fA mnA
(„Standard“ Spinel) (Hercynite) (Galaxite) Source: RHI

Raw materials
Raw materials used as matrix in basic bricks are the following:
Raw material Chemical Typical Comments

formula composition
Doloma MgO.CaO 56-62% MgO Sintering or fusion of natural
36-40% CaO dolomite (CaMg(CO3)2)
< 2% SiO2
Sintered MgO 85-99.8% MgO - Sintering of natural
magnesia 0.1-3.5% CaO magnesite (MgCO3) or
0.1-3% SiO2 Mg(OH)2 from seawater or
0.1-8% Fe2O3 brines (MgCl2)
< 0.3% B2O3 - Crystal size 60-200 µm
- Porosity of grains < 12%
Fused MgO 97-99.8% MgO - Fusion of magnesia
magnesia < 2% CaO - Crystal size 400-3000 µm
< 1% SiO2 - Porosity of grains < 2%
> 0.3% Fe2O3

Basic refractory - modifiers
Zirconia ZrO2
Spinel Group Zirconia has a very high melting

Spinel MgO•Al2O3 point of approximately 2’700°C.
Hercynite FeO•Al2O3 Three modifications exists similar to
quartz which have very different
Galaxite MnO•Al2O3 molar-volumes. To make ZrO2
Magnesioferrite MgO•Fe2O3 stable, MgO or CaO is needed.
Mg-Chromite MgO•Cr2O3 When it is subjected to liquid phase
Chromite FeO•Cr2O3 attack it forms high melting point
phase.

Magnesia-alumina phase diagram
Spinel is a very good elastifier – but it reduces refractoriness

Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 19

Shaped vs. unshaped products
shaped products unshaped products
• homogeneous product
• good product properties
low risk of defects
• quick lining method
Advantages • self-supporting lining (no
anchors!) • good for complicated
geometry (only few joints)
• quick heating up possible
• sensitivity of workability
• dependence on kiln size
Disadvantages and the construction • slower heat-up
design in static areas
• anchor corrosion

Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 21

Identification of Zones in PC, SP and Long Dry/Wet kilns
Zones:
 Drying zone: Water evaporation
 PZ: Removal of hydrate and chemically
bound water.
 CZ: Dissociation of carbonates
 UTZ: Formation of Liquid Phase
(unstable coating).
 SZ: Completion of C3S formation (stable
coating).
 LTZ: Clinker cooling starts (unstable
coating).
 Cooling zone: Freezing of liquid phase
(free of coating normally).
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Basic zones
Calcined
meal
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Fuels impact on burning zone
Taken from: H.Merker, Moderne Feuerfestauslegung von Drehofenanlagen mit AF- und AR-Produkten, Refratechnik, 2005
2014-08-20 © 2014 24
Kiln shell scanner diary
By courtesy : Oujda plant, Holcim (Marocco)
2014-08-20 © 2014 25
Principles of Brick choice
• Transition zones (upper and lower)
 Not permanently coated
 High thermal and chemical stress
 High %MgO (fused), lower Spinel content
 Limited thermal shock resistance, lower mechanical flexibility
• Central burning zone
 Permanently coated
 Better protected from thermo-chemical attack
 Lower %MgO, higher Spinel content
 Better mechanical flexibility
• Calcining zone
 No need for basic bricks
 Alumina bricks, SiC with regard to alkali load
CMC APAC Fall 2014, 2014-09-01 © 2014 26

Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 27

Rotating methods
• Advantages:
 Lining from 6 o’clock to 9 o’clock position
 Simple methods requiring few equipment

• Disadvantages
 Kiln must be rotated during installation
 Security risk if bricks are not fastened enough
 Ring tightening prior closing difficult
2014-08-22 © 2014 28
Example: Screw jack method
• Advantages:
 Easy, cheap
 Bricklaying in the optimum position
(6 and 9 o’clock position)
• Disadvantages:
 D < 4,4m. Danger of the screw-
jacks slipping.
 Kiln has to be rotated.
 Low bricking progress 14-16h/t
2014-08-22 © 2014 29
Formwork methods
• Advantages
 Kiln does not need to be rotated
 Particularly suitable for large kiln diameters
 Highest lining speed achievable
• Disadvantages
 Theoretical mixing ratio of different tapered bricks cannot be
followed, since curvature of kiln shell is flatter at the top and
narrower at the flanks
 Influence of floating tire fixation
 High initial investment.
 Pays off only for longer sections to line
 Most popular method today.
2014-08-22 © 2014 30
Example: Bricking machines
• Multi-O-Ring (Brokk), DAT (RHI), Refra Rig (Refratechnik)
2014-08-22 © 2014 31
Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 32

Shaped and unshaped refractories in static kiln parts
Taken from: H.Merker, Modern refractory layout of a new clinker burning unit,
Refratechnik, 2012
2014-08-20 © 2014 33
General lining design in static kiln section
Taken from: H.Merker, Modern refractory layout of a new clinker

burning unit, Refratechnik, 2012
2014-08-20 © 2014 34
Refractory material choice
Taken from: K.Beimdiek, Monolithic refractory system

solutions for installation technologies and linings of preheater
and cooler in cement plants, Refratechnik, 2012
2014-08-20 © 2014 35
Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 36

Encapsulated lining design
Taken from: K.Beimdiek, Monolithic refractory system solutions for installation

technologies and linings of preheater and cooler in cement plants, Refratechnik, 2012
2014-08-20 © 2014 37
Higher allowance for shell temperature
Accept higher heat loss!
2014-08-20 © 2014 38
Content
 Introduction
 General design
 General design
 AR concept
CMC APAC Fall 2014, 2014-09-01 © 2014 39

Installation methods
2014-08-20 © 2014 40
Dry gunning
• Material volumetric dosing,
pneumatic transport
• Passes a mixing nozzle
where water is introduced
• Used mainly for insulating
lining and for HCG and MCG
• Optimized water nozzles
allow also processing of
some LCG
• High rebound loss (10-50%)
• High dust formation
• Short reaction time between
water and cement and
incomplete mixing of water
and cement
2014-08-22 © 2014 41
Wet gunning = ShotCasting = JetCasting = ShotCreting
• Material is mixed with water already in a special
mixer and pumped as concrete to the nozzle,
where a setting accelerator (water glass or
sodium silicate) is added, to speed up setting
• Used for LCG and ULCG
• Equipment more sophisticated, more expensive
• Carried out by specialized contractors and in
case of bigger repairs (>50-100t) or new
installations
• Maximum transfer 40m, with additional pump up
to 80m
Taken from: K.Beimdiek,
Monolithic refractory system
solutions for installation
technologies and linings of
preheater and cooler in cement
plants, Refratechnik, 2012
2014-08-22 © 2014 42
Drying and Heating-up
• How to combine?
2014-08-22 © 2014 43

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Refractory

CMC APAC, Fall 2014, Michael Kapphahn EPT-TT

CMC APAC Fall 2014, 2014-09-01 © 2014

CMC APAC Fall 2014, 2014-09-01 © 2014 2

CMC APAC Fall 2014, 2014-09-01 © 2014 3

0 500 1000 1500 2000 2500 3000 3500 4000

CMC APAC Fall 2014, 2014-09-01 © 2014 4

CMC APAC Fall 2014, 2014-09-01 © 2014 5

CMC APAC Fall 2014, 2014-09-01 © 2014 7

high-alumina products fireclay products The formation of the first

CMC APAC Fall 2014, 2014-09-01 © 2014 8

The refractoriness of alumina

High refractoriness and high alkali resistance compete in an alumina-silica

CMC APAC Fall 2014, 2014-09-01 © 2014 9

CMC APAC Fall 2014, 2014-09-01 © 2014 10

CMC APAC Fall 2014, 2014-09-01 © 2014 12

CMC APAC Fall 2014, 2014-09-01 © 2014 13

Refractory Seminar 2013 © 2014 14

Refractory Seminar 2013 © 2014 15

Raw material Chemical Typical Comments

Refractory Seminar 2013 © 2014 16

Spinel Group Zirconia has a very high melting

Refractory Seminar 2013 © 2014 17

Spinel is a very good elastifier – but it reduces refractoriness

CMC APAC Fall 2014, 2014-09-01 © 2014 19

Refractory Seminar 2013 © 2014 20

CMC APAC Fall 2014, 2014-09-01 © 2014 21

By courtesy : Oujda plant, Holcim (Marocco)

CMC APAC Fall 2014, 2014-09-01 © 2014 26

CMC APAC Fall 2014, 2014-09-01 © 2014 27

 Simple methods requiring few equipment

CMC APAC Fall 2014, 2014-09-01 © 2014 32

Taken from: H.Merker, Modern refractory layout of a new clinker

Taken from: K.Beimdiek, Monolithic refractory system

CMC APAC Fall 2014, 2014-09-01 © 2014 36

Taken from: K.Beimdiek, Monolithic refractory system solutions for installation

CMC APAC Fall 2014, 2014-09-01 © 2014 39

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