refractory application for extreme firing condition in … application for extreme firing condition...
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Refractory application for extreme firing condition
in the regenerator of glass melting furnaces
Sandra Fischer, Rongxing Bei, RHI Glas GmbH, Germany
For part of “thermal chemical regenerator”: Joaquín de Diego, Praxair, Inc., USA
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, October 22-25th 2017
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Content
• Pet-coke firing
• Sodium silicate glass
• Thermal chemical regenerator
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Content
• Pet-coke firing
• Sodium silicate glass
• Thermal chemical regenerator
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
Cr2O3 11.9 9.0 1.1
Fe2O3 24.9 14.3 20.9 11.0 9.8
NiO 7.6 6.7 6.7 4.4
V2O5 30.1 7.3 29.3
From the pet-coke ash:
High amount of Cr, Fe, Ni, and V
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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V2O5 total in flue gas (Kg / ton glass)
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Problem for glass production The unburned pet coke powder can go into the regenerator,
A re-firing within regenerator can happen:
High temperature and strong thermoshock
Destruction of the regenerator crown, wall and checker
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Magnesia Zircon (RUBINAL VZ) :
Forsterite formation during brick production
ZrSiO4 + 2MgO Mg2SiO4+ ZrO2
Protection of the Periclase (1) by matrix out of Forsterite and ZrO2
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Example Magnesia zircon brick (Rubinal
VZ) shows corrosion of half
layer after 6 years
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Corrosion Test
Hot face not corroded
excellent resistance against carryover and V2O5
Chrome corundum with 10% Cr2O3 (DURITAL RK10)
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Corundum (1) is protected by chrome corundum solid solution (2)
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Pet-coke firing
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Checker Lining Recommendation
Top Layer: Magnesia Zircon and Chrome Corundum
Hot zone (>1100 °C): Magnesia Zircon
DURITAL RK10
RUBINAL VZ
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Content
• Pet-coke firing
• Sodium silicate glass
• Thermal chemical regenerator
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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Component ratio
SiO2 : Na2O
Name
3,9 to 4,1 High silicic acid water glass
3,3 to 3,5 Neutral soda glass
2,0 to 2,2 Basic water glass
Sodium silicate (water glass):
Amorphous melts of alkali silicates
Waste Gas containing:
NaOH (gas firing)
Na2SO4 (oil firing)
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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For gas firing:
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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Gas firing:
Condensation zone,
MgO (ANKER DG1)
After 5 years
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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NaOH had no effect on MgO – it entered
the Magnesia-crystal to form a „ring“ on
the surface
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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Oil firing:
Condensation zone,
magnesia-Zircon
After 12 years
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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1: cavity
A and B:
matrix of forsterite and
ZrO2
C: ZrO2
Even after 12 years of
application the matrix
has done a good job!
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Sodium silicate glass
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Content
• Pet-coke firing
• Sodium silicate glass
• Thermal chemical regenerator
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Process of thermochemical regenerator
CH4, H2O, CO2, CO and H2 exist in
different height of checker work
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Test setup
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Test setup
Different refractory samples
• installed in doors
• installed in ports
• for 8 months
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Refractories in the temperature-range of 1150-1200°C
All wall samples containing
mullite:
zirconia mullite
fused mullite
sintered mullite
are damaged!
Reason:
Na2O (out of waste gas) +
Mullite
Nepheline formation
zirconia mullite
Baddeleyite, syn ZrO2 +++
Corundum, syn Al2O3 +++
Mullite, syn Al6Si2O13 +
Nepheline NaAlSiO4 +
SO3 0,30
Na2O 4,16
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Refractories in the temperature-range of 1150-1200°C
Checker sample
in TCR
Magnesia and
magnesia zircon:
• no interaction with Na2O
• no damage
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Magnesia 97
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Refractories in the temperature-range of 1150-1200°C
What is important for magnesia with C2S-bonding?
MgO-MgO-direct bonding!
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Case Example
Magnesia 97
direct bonding
Magnesia 97 direct bonding used as checker in one float furnace:
• 14 years
• Firing with heavy oil and gas
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Case Example
Magnesia 97
direct bonding
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Case Example
2CaO.SiO2 disappeared (corroded by Na2O and V2O5)
MgO-MgO direct bonding
remains (circles)
Magnesia 97
direct bonding
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Conclusion
Pet-coke firing (Vanadium attack):
• Magnesia zircon (RUBINAL VZ) has good performance.
• Chrome corundum (DURITAL RK10) even better
Sodium silicate glass (Strong NaOH attack):
• Magnesia zircon (RUBINAL EZ) for oil firing
• Magnesia (ANKER DG1) for gas firing
Thermal chemical regenerator:
(Changing between reducing and oxidising atmosphere):
• Basic materials showed no attack
• MgO-MgO direct bonding is important
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Refractory for extreme firing condition in regenerator
2017 ICG Annual Meeting & 32nd Şişecam Glass Symposium, Istanbul, Oct 22-25th 2017
Thank you for your attention
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