GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company Sulphur Recirculation CUTNOX NextBAT Sulphur Recirculation for reducing corrosion and increasing electrical efficiency in WtE boilers Dr. Sven Andersson Götaverken Miljö AB, Sweden – a Babcock & Wilcox Vølund company
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GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Sulphur Recirculation for reducing corrosion and increasing electrical efficiency in WtE boilers
Dr. Sven Andersson
Götaverken Miljö AB, Sweden– a Babcock & Wilcox Vølund company
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBATSulphur RecirculationOperating principlesFull-scale operationAshes and depositsEmissionsCorrosion rates
Ash
Sulphur Recirculation
Sulphur in fuel
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
The effect of chromium depletion on chromia forming steels
(Cr,Fe)2O3 Fe2O3 + K2CrO4 + HClO2 + H2O + KCl
Before After
Chromate formed
KC
lK
2CO
3K
2SO
4Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
304L (Fe20Cr10Ni), 5% O2 + 40%H2O, 600°C
O2 (no salt)
Pettersson, J., Folkeson, N., Johansson, L.-G., Svensson, J.-E., The Effects of KCl, K2SO4, and K2CO3 on the High Temperature Corrosion of a 304-Type Austenitic Stainless Steel. Oxidation of Metals, 2011. 76(1): p. 93-109.
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
The effect of chromium depletion on chromia forming steels
(Cr,Fe)2O3 Fe2O3 + K2CrO4
O2 + H2O + K2CO3 + CO2
Before After
Chromate formed
Chromate formed
KC
lK
2CO
3K
2SO
4Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
304L (Fe20Cr10Ni), 5% O2 + 40%H2O, 600°C
O2 (no salt)
Pettersson, J., Folkeson, N., Johansson, L.-G., Svensson, J.-E., The Effects of KCl, K2SO4, and K2CO3 on the High Temperature Corrosion of a 304-Type Austenitic Stainless Steel. Oxidation of Metals, 2011. 76(1): p. 93-109.
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
The effect of chromium depletion on chromia forming steels
(Cr,Fe)2O3 Fe2O3 + K2CrO4O2 + H2O + K2SO4 + SO2
Before After
Chromate formed
Chromate formed
KC
lK
2CO
3
No chromate formedK
2SO
4Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Exposure time (h)
0 24 48 72 96 120 144 168
Mas
s ga
in (m
g/cm
2 )
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
304L (Fe20Cr10Ni), 5% O2 + 40%H2O, 600°C
O2 (no salt)
Pettersson, J., Folkeson, N., Johansson, L.-G., Svensson, J.-E., The Effects of KCl, K2SO4, and K2CO3 on the High Temperature Corrosion of a 304-Type Austenitic Stainless Steel. Oxidation of Metals, 2011. 76(1): p. 93-109.
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
SNCR
Dosage
Oil burn.
Grate
Super-Heaters
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Full-scale tests at Renova P5 (Göteborg)
V
Dosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage
Con
dens
ing-
scru
bber
Bag houseRe-heat
Stac
k
Sulphuric acidAtomization air
H2O2
Flue gas recirculation
22 ton waste/h
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Full-scale tests at Renova P5 (Göteborg)
V
Dosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage
Con
dens
ing-
scru
bber
Bag houseRe-heat
Stac
k
Sulphuric acidAtomization air
Flue gas recirculation
22 ton waste/h
SO2
H2SO4
SO2
H2O2
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
1000 h Reference (normal operation)
V
Furnace
ESP Eco
SO2-stage
HCl-stage
Con
dens
ing-
scru
bber
Bag houseRe-heat
Stac
k
H2O2
1000 h Reference: SO2 in boiler = 270 mg/m3 (n,dg)
SO2 in boiler
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
1000 h Recirculation: SO2-setpoint
V
Furnace
ESP Eco
SO2-stage
HCl-stage
Con
dens
ing-
scru
bber
Bag houseRe-heat
Stac
k
H2O2
1000 h Reference: SO2 in boiler = 270 mg/m3 (n,dg)1000 h Recirculation: SO2 in boiler = 720 mg/m3 (n,dg)
SO2 dosage
SO2 in boiler
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Sampling and measurements
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Deposit rate (g/m2,h) decreased with SO2
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.Acid dew point measurements
0
10
20
30
40
50
60
0 200 400 600 800 1000
Dep
osit rate (g/m
2 ,h)
SO2 (mg/Nm3)
Ref
Recirk
Impactor and deposits probe
Short term meas.
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Fly ash Cl/S vs SO2 from 3 different plants
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.
0.0
1.0
2.0
3.0
4.0
5.0
6.0
0 200 400 600 800 1000
Cl/S
SO2 after boiler(mg/Nm3 t.g.)
Fly ash
Reference
Optimisation
Recirculation
TAMARA
Plant B
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Acid Dew point Temperature (ADT)
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.
Sulphur Recirculation
Lancom 200 Acid Dewpoint Monitor
Result: No measurable ADT
Detection limit: 110-120°C
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Dioxins in the flue gas: ¼ less
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.
AMESA continuousdioxin sampler
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
2
Ref 1‐3 Ref 4 Recirk 1‐3
I‐TEQ
ng/Nm3@
11O2
Ref Ref Recirc
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
time (days)
Mon
21
Tue
22
Wed
23
Thu
24
Fri 2
5
Sat 2
6
Sun
27
Mon
28
Tue
29
Wed
30
Thu
01
Fri 0
2
Sat 0
3
Cl/S
(HC
l, SO
2)
0.01
0.1
1
10PC
DD
/F (T
EQ n
g/N
m3 , 1
1% O
2)
0.01
0.1
1
10
Sulphur Recirculation
Dioxins
Cl/S
Start-up
Dioxins in raw gas ~ emission limit!
Pilot tests at KIT – Dioxin reduction
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Stack values (% of Emission limit)
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.Emission meas.
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Boiler ash ESP ashAsh samplingDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kAcid dew point measurements
High temp corrosion probe 24 h and 1000 h Impactor and deposits probe
AMESA continuousdioxin sampler
Emission meas.High temp corrosion probe 24 h and 1000 hImpactor and deposits probe
Corrosion probes in the superheater position
Sulphur Recirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBAT
Corrosion probes in the superheater position
(wt%) Cr Ni Mn Si Mo Fe nCr/nFe Add. elements16Mo3 - - 0.6 - 0.3 99.1 0 -