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CO2 Emission Reduction Potential andTechnological Aspects of the Oxyfuel Technology in Cement Clinker Production
Dr.-Ing. Volker Hoenig, Dipl.-Ing. Kristina KoringOCC3 Ponferrada September 2013OCC3, Ponferrada, September 2013
AGENDA
1 Clinker burning process
2 Integration of the Oxyfuel Technology and design aspects
3 I t l t ti3 Impact on plant operation
4 Impact on material conversion and product quality
5 Cost estimation
6 Summary and Outlook
1. Introduction - Clinker burning process
Flue gas300 - 350 °C Material CO
Raw meal
Cyclone
300 350 C Material CO2
Fuel CO2CaCO3, SiO2, Al2O3, Fe2O3
Cyclonepreheater
Calciner
Cooler exhaust air
Tertiary air ductFuel/air
Fuel
700 - 1000 °C
200 °C - 350 °C
850 °C
700 - 1000 °C
Cooling air
Rotary kiln 2000 °C
700 1000 C
Clinker
CaCO3 CaO + CO2
Coolerg Clinker
2. General layoutHeat
exchangerBag filter
CO2 rich flue gas
Storage
Raw Material
Transport
CO2 Compression
Mixing gas
Exhaust air cleaning
Pre-heater
Raw Mill
Fuel Preparation
Fuel
CO2 Purification
Condenser
Rotary Kiln
Pre-calciner
Air In-leaks
Air
Rotary Kiln
Cooler Clinker
Oxidizer
Air Separation
Unit NGas Mixing
AirOxidizerUnit N2
2. Retrofitting boundaries
• Important aspect for the application of oxyfuel in Europe
• Retrofitting an existing burner for oxyfuel application is unlikely, but replacement by a suitable design is possible
• Designing a gas-tight two-stage cooler is feasibleDesigning a gas tight two stage cooler is feasible• False air intrusion could be reduced to the greatest
possible extent by overhauling/ replacing inspection doors and similar devices (< 6%)
• New safety and controlling devices necessary • Space requirements of ASU/CPU• Conventional behavior in trouble shooting restricted
(no opening of doors/flaps in the plant etc )(no opening of doors/flaps in the plant etc.)
Retrofitting is feasible
3. Impact on plant operation
• Air separation andCO2 purification areenergy intensive
• Influence on heattransfer andtemperature profiles gy
• Energetic integrationrequired
p p• Adaptation of plant
operation necessary
Gas Add. Plant Aggre-Property Aggre-gates
• New installations• Recirculation rate: F ti f t t l fl
Plant Modifica-
tionRecircu-
lation rate• Retrofitting existing
plantsFraction of total fluegas, which isreciculated to process
• Setting of oxygen level
tion
3. Impact of gas properties
Stress on2200 ∆ 50 - 100 C Stress on refractory
1800
2000
2200
tur [
°C]
n °C
1200
1400
1600
Gas
tem
pera
tem
pera
ture
i
1000
1200
Ofenlänge
G
∆ 150 C
Kiln length
Gas
te
Potential increase of
OfenlängeReferenz: Luftbetrieb Rezirkulierung, 21 Vol.-% O2Rezirkulierung, 25 Vol.-% O2 Rezirkulierung, 23 Vol.-% O2O2
O2O2
Reference: Air operationRecirculation Recirculation
Recirculation
Potential increase ofcoating formation
3. False air ingress and flue gas composition
87
88
Influencing parameters:
O
85
86
n flu
e ga
s [v
ol.%
] • Oxygen purity
• False air ingress
• Oxygen excess
83
84
2-co
ncen
tratio
n in • Oxygen excess
• Fuel type
81
82
1 2 3 4 5 6 7 8 9 10
CO
2
False air reduction of 6 - 8 % technicallyfeasible by improved maintenance withoutadditional sealing methods (like e.g. waste
air-ingress [% of flue gas]
Oxidizer: 95 vol.% O2, 3.5 vol.% O2 excess
Oxidizer: 98 vol.% O2, 3.5 vol.% O2 excess
Oxidizer: 99.5 vol.% O2, 3.5 vol.% O2 excess
g ( ggas flushed systems)
3. Flue gas recirculation
3100
3150Plant modificationsnecessary due to
3000
3050
3100
Ene
rgie
beda
rf g
Klin
ker
yreduced volume flow
in preheater
yde
man
din
ker
2900
2950
3000
Ther
mis
cher
Ein
kJ/
kger
mal
ene
rgy
in k
J/kg
cl
2850
2900
0,3 0,35 0,4 0,45 0,5 0,55 0,6
Rezirkulationsrate
T
Recirculation rate0.3 0.35 0.4 0.45 0.5 0.55 0.6
The
Fuel energy demand is depending on flue gas recirculation and treatmentD i i l ti t i l d l fl l
RezirkulationsrateRecirculation rate
Decreasing recirculation rate includes less flue gas losses
3. Energetic consideration
850
950
ker
650
750
850
kJ/k
g K
linke
r Power generationRaw material drying
in k
J/kg
clin
k
450
550
enth
alpi
e in
External heatexchanger
as e
ntha
lpy
i
250
350
0,3 0,35 0,4 0,45 0,5 0,55 0,6
R i k l ti t
Gas
0.3 0.35 0.4 0.45 0.5 0.55 0.6
Ga
Rezirkulationsrate
Abgas Vorwärmer Kühlerabgas, Stufe 2
Recirculation rate
Flue gas, preheater Cooler exhaust air
Recirculation rate determines the energy distribution andtherefore waste heat recovery potential
3. CO2 emission reduction potential
Capture rates of 88 to 99 % feasible Capture rate independent of recirculation rate Reduction of capture rate possible by
Exhaust gas of the CO2 purification unit (- 1 to 10 % capture) Additional firing for raw material drying (- 1 to 2 % capture) Leakage at cooler stage sealing (up to - 1 % capture)
RezirkulationRezirkulationRecirculation
Abluft von der CPUAbluft von der CPU
Exhaust gas ofCPU
Entsäuerung
Primärgas
CO2 zum Speicher
Kühl bl ft
Entsäuerung
Primärgas
CO2 zum Speicher
Kühl bl ft
Calcination
Primary gas
CO2 forstorage/reuse
BrennstoffKühlerabluft
mögliche Zufeuerung
BrennstoffKühlerabluft
mögliche Zufeuerung
FuelCooler leakagePotential additional
firing
4. Kiln operation – Impact on solid conversion
60
70
40
50
60
[wt.%
]
20
30
olid
con
tent
0
10
s
kil l thkiln length
Reference, C3S Reference, C2S
Recirculation 21 vol.% O2, C3S Recirculation 21 vol.% O2, C2S
Recirculation 23 vol.% O2, C3S Recirculation 23 vol.% O2, C2S
4. Limiting factors by quality and durability requirements
• No serious influence on clinker composition • Slight differences in cement properties
(caused by Fe2+) are in range of assured(caused by Fe2+) are in range of assured quality
• No negative influence on basic refractory material detectedmaterial detected
• Using non-basic materials an increasing thermo-chemical reaction expected
• Adaption of refractory brickwork necessaryp y y• Long-term test for evaluation advisable
14000
[49-442] Ca3SiO5[33-302] Ca2SiO4 / Larnite
[30-226] Ca2(Al,Fe)2O5 / Brownmillerite[38-1429] Ca3Al2O6 (cubic)
[32-150] Ca3Al2O6 (ortho)[45-946] MgO / Periclase
[37 1497] C O / Li
von unten nach oben:V1K1, 2011-i_MVT-03280V6K1, 2011-i_MVT-03285V11K1, 2011-i_MVT-03290V16K1, 2011-i MVT-03295
2000
4000
6000
8000
10000
12000
Abs
olut
e In
tens
ity
[37-1497] CaO / Lime[37-1496] CaSO4 / Anhydrite[46-1045] SiO2 / Quartz, syn
[49-1807] Ca5(SiO4)2SO4 / TernesiteP-2011/0372, A11/057 (Range 1)
V16K1, 2011 i_MVT 03295V21K1, 2011-i_MVT-03305V26K1, 2011-i_MVT-03310
No barriers expected from clinker quality and refractory
durability2Theta10.0 20.0 30.0 40.0 50.0 60.0
0
2000 durability
4. Impact on decarbonation
1
Increase of temperature level:
• Problems with 0,6
0,8
arbo
natio
n [-] Conventional
operation
burning low-calorific fuels in calciner may occur
0 2
0,4
degr
ee o
f dec
a ∆ 80 K
• Higher risk of coating formation in the calciner0
0,2
650 700 750 800 850 900 950 1000
d Oxyfuel operation
temperature [°C]
pCO2 = 0,2 bar pCO2 = 0,4 bar pCO2 = 0,6 barpCO2 = 0,8 bar pCO2 = 0,97 bar
4. Impact on cement properties
120
105
110
Strenght developmentSetting behaviour
60
80
100
stre
ngth
in %
85
90
95
100
heat
in % %
20
40
60
com
pres
sive
65
70
75
80
85
hydr
atio
n
0
Standard condition Oxyfuel condition
2 days 28 days
60
65
Standard Conditions Oxyfuel ConditionsBurning: CO2/ Cooling:Standard Burning: Standard/ Cooling: CO2
samples 1 -5 after 48 h
Standard condition Oxyfuel conditionBurning: CO2/ Cooling: Standard Burning: Standard/ Cooling: CO2
Burning: CO2/ Cooling:Standard Burning: Standard/ Cooling: CO2
Testing at five clinker types of different reactivity No influence on chemical-mineralogical composition Cement properties are not influenced
5. Cost Estimation
New installation (2 mio tpy annual clinker capacity):
2030: 330 - 360 Mio € (Reference: 260 Mio €)
Investment costs
2030: 330 - 360 Mio € (Reference: 260 Mio €)
2050: 270 - 295 Mio €Remark: Costs for demonstration plant in 2020 would be significantly highersignificantly higher
Operational costsFixed operating costsRaw materials Misc
plus 8 to 10 €/tclinker on top of base casetransport and storage excluded
Coal
Power
Total cost increase of about 40 %
Additional costs per ton of avoided CO2 : 33 - 36 €/t CO2
6. Summary and Outlook
Oxyfuel technology in the cement clinker burning process technically feasible
Retrofit of existing plants is possible Cement properties are not impaired Optimum operational mode depends on local specification of the cement Opt u ope at o a ode depe ds o oca spec cat o o t e ce e t
plant (e.g. raw material moisture) Capture rate between 88 and 99 % Production costs are increased by 40% (excl transport and storage) Production costs are increased by ~ 40% (excl. transport and storage) Oxyfuel technology will not be available in the cement sector before
2030 ECRA CCS Project Phase IV.A is dealing with the further detailing of
previous phases and the concept study of an oxyfuel pilot plant
Thank you for the attention!
www. ecra-online.org