Gouda Refractories 11 June 2015 AMAP Colloquium

6-7-2015
Refractories for aluminium

the industry behind the industries
the theory behind the refractories
AMAP colloquium 11 June 2015

ir. drs. Marcel C. Franken
www.goudarefractories.com
General
Any process at high T in a installation
need for refractory (Feuerfest)
• not only resistent to high temperatures (Feuer)
• resistent to interaction with process
• keep heat in installation
Process
miniumum
high T
heat loss
refractory
no interaction
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6-7-2015
In a process installation many

partial processes
each partial process different
refractory solutions possible:
bricks, castables, chemical
composition,….
PROCESS
Search
for the perfect match
REFRACTORY
“each advantage has its disadvantage”
Refractory industry - “industry behind industries”

Refractory Consumption in Consumers Industry of Europe
Steel
65%
Chemical and Cement/Lime

Others Non-ferrous Glass 8%
18% 4% 5%
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Refractory consumption
Specific consumption in 1955, 1980, 2000 and 2010 in major industries :
Specific consumption Reduction
kg (refractory) per t * (product)
1955 1980 2000 2010 Total in %
Iron and Steel 50 30 18 16* 68
Cement, Lime 2,2 1,2 0,9 0,7 68
Glass 15 12 6 5 66
Aluminium 25,5 20 14 10 60
* Japan 11, Europe 12, USA 12, China 30 kg/ton
Reduction refractory consumption:

• improved process control
• larger installation (A/V)
• improved refractory
Refractory producers
In Europe 26.000 employees and
turnover 3.1 billion Euro
Tendency conglomeration:
• RHI Refractories:
Didier, Veitsch, Radex, Harbison&Walker
• Vesuvius:
Premier, VGT-Dyko
• Saint Gobain:
Carborundum, Savoie, Norton
• Calderys:
Lafarge, Plibrico
…….
Gouda Refractories (Vuurvast)

Private owned company since 1901
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Gouda Refractories
Total refractory lining solutions for critical
equipments in various industries (% of TO)
Aluminium 45 %
Petrochemical 35 %
Power & Energy 55 %
Steel 5%
Calcination 10 %
Global network
Manufacturing, design, installation

65.000 ton bricks, 25.000 ton castables, 2500 ton precast (range: 30-100% Al2O3)
Refractory is chemistry and physics

“alchemistry”
Basis chemistry:
• inorganic material
• oxidic components
• reactions “transformations”
Basis physics:
• material expands as it becomes hot
Refractories goes to the fire
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Thermal expansion
Back to basic
Stable oxides
High melting temperature
Classification based on chemistry
Slagbasicity: CaO/SiO2
Basic Product Alumina-silicates Special Product

Magnesia “acid” product Graphite/Carbon
not used
MgO-Cr2O3 Silica ZirconSpinel
reaction with Al
Chromite Chamotte (Fire clay) Siliciumcarbide
spinel formation
Doloma
high expansion Sillimaniet/Andalusiet/Kyaniet/Mulliet Siliciumnitride
Forsterite Sinterbauxiet SiAlON
Corundum
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6-7-2015
Al2O3-SiO2 Phasediagram
each material has its

own properties:
refractoriness,
chemical resistance,..
Silica Chamotte Andalusite Bauxite Corundum

Sillimanite
Kyanite Mineral name vs chemical composition
Mullite
Al2O3-SiO2 Phasediagram
Name of product
Temperature, eg
Curon 160= 16000 C
Group 23 = 2300 F
percentage Al2O3, eg AK46, AK85

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6-7-2015
What is refractory ?
Grain Size Distribution:
“flow” properties and density
Grain type:
“chemical” properties
Due to grains: high compressive

strength, less tensile strength (5:1)
Brick Castable
clay bonding cement bonding
(ceramic /phophate)
ready to use semi-product
is mixed, densified, fired made on site
Raw materials: Bauxite

Origine: Les Baux-en-Provence (F)
Consists of boehmite (Al2O3.H2O) and/or gibbsite (Al2O3.3H2O).
For refractory high Al2O3 and low impurities
Dig up (aluminiumhydrate), drying and firing/sintering 1400-1600 °C

in rotary- or shaftkiln, porosity 12-20 %
Sintered bauxite mineralogy: corundum, mullite, tialite and glass
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6-7-2015
Raw materials: Bauxite China Guyana

Bauxite Bauxite
Al2O3 84 – 89% 84 – 89%
SiO2 6 – 10% 6 – 10%
TiO2 3 – 4,5% 2 – 3,5%
Fe2O3 1,5 – 2,5% 1,5 – 2,5%
CaO + MgO < 0,5% < 0,1%
Na2O + K2O < 0,5% < 0,2%
Abrasion Good Minor
Resistance
Aluminium Minor Good
resistance
Chemical similar
but different properties
Manufacturing Refractory Brick

Castables are “semi”-products
quality made during
transport
installation
Sieve
Band Silo
Raw materials
Silo
Press
Sieve Pressed
Band Mixer Dosing brick
Elevator Kiln
Milling Elevator car
Green (unfired ) bricks
Dryer
Tunnelkiln Fired brick
Heating Firing Cooling
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6-7-2015
Refractory cement
Bonding of castable: CaO-containing PORTLAND
CEMENT CALCIUM ALUMINATE
(CS Cement) CEMENT
(CA Cement)
Differs from civil concrete:
calciumaluminate vs calciumsilicate
CA type 40% CAC 50% CAC 70% CAC

strength
Al2O3 37,5 – 41,5 50,8 – 54,2 68,7 – 70,5

CS CaO 36,5 – 39,5 35,9 – 38,9 28,5 – 30,5
SiO2 4,2 - 5,0 4,0 – 5,5 0,2 – 0,6
FeO+Fe2O3 14,0-18,0 1,0 – 2,2 <0,4
1 28
days Temp 1100 C 1300 C 1500 C
Types of castables
conventional castables low cement castable
(regular cement, RCC) (deflocculated – low cement, LC,ULC, NC)
Mixing
very critical
Impurities very critical
• cement content 15 - 20 % • cement content +/- 5 %
• fine fraction 0 - 0,5 mm • ultrafine fraction upto 0,3 um
• water added +/- 12 % microsilica – round spheres
• water added +/- 5 %
Ball in Hand method Vibrating method Self flowing
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6-7-2015
Castables become more dense (higher strength, more fines)

risc on steamexplosions
Explosion:
Water/vapor pressure > tensile stress refractory
Attack mechanisms wear of refractory

4 types:
• melting - liquidification of refractory, too high T
• spalling - “breaking” refractory due to ΔT (+ or -)
• corrosion - chemical attack
• erosion - abrasion, strength
Oft combination of mechanisms: MECHANICAL • abrasion

• stresses
no individual failure but amplifying 3
• weakening
each other (1+1=3) • therm expansion
• thermoshock spalling • cracks
also known as cause for wear (failure mechanism):
1 1
- CHEMICAL: corrosion THERMAL CHEMICAL
- THERMAL: melting and spalling • softening,
melting
• slag
• transformation
• reactions with
- MECHANICAL: erosion and spalling • reaction kinetic slag and gass
• lowering meltpoint
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6-7-2015
Thermodynamics
refractory (Al2O3-SiO2) can react with Al
Corundum formation:
4Al+SiO2 2Al2O3+3Si
2Mg+SiO2 2MgO+Si
Mg+2Al + 2SiO2 MgAl2O4+Si
4Al+3TiO2 2Al2O3+Ti
volume change and destroying refractory
Al2O3-SiO2 used:
• good thermal properties
• reasonable chemical resistance
• “low” cost
diamond is thermodynamical NOT stable
Thermodynamics
Tabular cement castable (no SiO2) usable?
CaO will not react with Al

3CaO + 2 Al 3 Ca + Al2O3 ΔG=+ 234 kJ
But:
3CaO + 8 Al Al2O3 + 3Al2Ca ΔG= - 234 kJ
seems like corundum formation but is
intermetallic formation
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6-7-2015
Reaction kinetic speed of reaction

Not only important if components reacts wich each other
but also the velocity (speed) of reaction
Lower temperature will give slower reaction
“Best refractory is water”

Keep process cold kinetics will be slowed
In aluminium
freeze line (solidification T) is at 2/3 of the hot face lining
Take care : change of Al-alloy – change of T solid?
T-profile calculations – thermal resistance (d/λ)
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6-7-2015
T-profile calculations – thermal resistance (d/λ)
More insulation - less heat loss
T-solidification
Disadvantage:
Temperature
• Less T-profile over wear lining

• Solidification-T deeper in lining
• More attack
• Risc of Al- outbreak
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6-7-2015
Change of Al-alloy (T-solid)
T-solidification
Temperature
Lower T-sol
Change Al-alloy to lower solidification

temperature risc of outbreak
Reaction kinetics – less surface

minimize surface reactions (less penetration by)
• lower porosity
• decrease wettability
use of anti-wetting agents:

• CaF2 equation of capillary action:
h=2γcosθ/ρgr
• BaSO4 Where:
• …. h - height the liquid is lifted,
γ - liquid-air surface tension,
Potential disadvantage: ρ - density of the liquid,
r - radius of the capillary,
• CaF2 lowers melting T reduction in strength at g - acceleration due to gravity,
T>900 C θ -the angle of contact
• BaSO4 decomposes (disappears) T>1150 C
Take care: change of Al-alloy – change of wettability?

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6-7-2015
Corrosion by Aluminium
Cup test, 72 hours
1050 °C 1200 °C
Figures are indicative (not typical Gouda Refractories products)
Critical T> 1100 °C, some additives “disappear”
Melting furnace T higher than holding furnaces
Often problems at burners (regenerative)
Effect of Al-alloy on refractory

Cup test, 72 hours, 1050 °C
Alloy 5083, Mg-rich Alloy 7020, Zn-rich

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6-7-2015
Melting & Holding Furnaces
Lining Posibilities
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6-7-2015
Melting and Holding Furnaces

Continuous push for more metal output
Higher operational temperatures
More mechanical abuse
More thermal shock
Increase of different alloys
More recycling of scrap
Higher performance requirements of refractories
Failure Mechanisms
Thermal stresses
• Due to charging of the furnace there are in some areas of the
furnace serious temperature fluctuations.
• The critical area’s are doorjambs and lintel
Abrasion resistance
• Charging of the furnace with big pieces of aluminium.
• Cleaning of the furnace with heavy equipment
Refractory design
• Refractory material with good thermal shock resistance/low thermal
expansion (mineralogy)
• Refractory material with high abrasion resistance / castable good
installation
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6-7-2015
Improve refractory to adapt to changing process
Gouda Refractories has many products:
>100 types of bricks (dense, insulating)
> 50 types of mortar (air, heat setting)
>400 types of castables (dense, insulating)
>100 type of precast blocks (dried, fired)
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6-7-2015
Refractory – General
Life time determined by:
• Quality - material and installation
• Design - good quality on the right place “zoning”
• Handling - (ab)use of refractories during operation
Gouda Refractories has many products, good refractory

know-how but limited process know-how
Only by mutual effort (user and supplier) and several disciplines

(process/operator, engineering,installation, refractory), it is possible
to improve lining and to obtain “best value in use”.
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6-7-2015
You know all about the process,

I will give you some information on refractories
or better give the theory behind refractories
so you better choose (know) your refractory for your
process
Or know the pros and cons of the refractory
“each advantage has its disadvantage”
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6-7-2015
INTEGRATED REFRACTORY APPROACH

Best value in use:
• Life time, installing time, repair time
• Availability Process
• Capacity
• Safety & health
• Environment
• …… Refractory Construction
material Engineering
Focus:
not on price per ton refractory but “best value in use”
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6-7-2015
Material choice
• know process conditions
• know material properties
match material on process (and vice versa)
Search
Application PROCESS
for the perfect match
Properties
REFRACTORY
Chemical composition Microstructure
22

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What are some of the major industries that use refractories?

What are some of the major industries that use refractories?

How has the specific refractory consumption reduced over time in major industries?

How has the specific refractory consumption reduced over time in major industries?

6-7-2015

Refractories for aluminium

AMAP colloquium 11 June 2015

In a process installation many

Refractory industry - “industry behind industries”

Chemical and Cement/Lime

Reduction refractory consumption:

Gouda Refractories (Vuurvast)

Manufacturing, design, installation

Refractory is chemistry and physics

Classification based on chemistry

Basic Product Alumina-silicates Special Product

each material has its

Silica Chamotte Andalusite Bauxite Corundum

percentage Al2O3, eg AK46, AK85

Due to grains: high compressive

Raw materials: Bauxite

Consists of boehmite (Al2O3.H2O) and/or gibbsite (Al2O3.3H2O).

For refractory high Al2O3 and low impurities

Dig up (aluminiumhydrate), drying and firing/sintering 1400-1600 °C

Sintered bauxite mineralogy: corundum, mullite, tialite and glass

Raw materials: Bauxite China Guyana

Manufacturing Refractory Brick

Green (unfired ) bricks

Tunnelkiln Fired brick

Heating Firing Cooling

CA type 40% CAC 50% CAC 70% CAC

Al2O3 37,5 – 41,5 50,8 – 54,2 68,7 – 70,5

Ball in Hand method Vibrating method Self flowing

Castables become more dense (higher strength, more fines)

Attack mechanisms wear of refractory

Oft combination of mechanisms: MECHANICAL • abrasion

volume change and destroying refractory

CaO will not react with Al

Reaction kinetic speed of reaction

Lower temperature will give slower reaction

“Best refractory is water”

T-profile calculations – thermal resistance (d/λ)

T-profile calculations – thermal resistance (d/λ)

More insulation - less heat loss

• Less T-profile over wear lining

Change of Al-alloy (T-solid)

Change Al-alloy to lower solidification

Reaction kinetics – less surface

use of anti-wetting agents:

Take care: change of Al-alloy – change of wettability?

Effect of Al-alloy on refractory

Alloy 5083, Mg-rich Alloy 7020, Zn-rich

Melting & Holding Furnaces

Melting and Holding Furnaces

Higher performance requirements of refractories

Improve refractory to adapt to changing process

Gouda Refractories has many products:

>100 types of bricks (dense, insulating)