Sulphur Recirculation for reducing corrosion and ......GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox...
Transcript of Sulphur Recirculation for reducing corrosion and ......GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox...
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
Sulphur Recirculation CUTNOX NextBATCUTNOXOperating principlesFull-scale installationNOx reduction
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Sulphur Recirculation CUTNOX NextBATNextBATHCl / SO2 / NH3HgDioxinsNOxFine particlesEnergy recovery
CUTNOX™ in combination with SNCR
SulphurRecirculation
GÖTAVERKEN MILJÖ AB – a Babcock & Wilcox Vølund company
Sulphur Recirculation CUTNOX NextBATElectricity production in WtEis limited by superheater corrosion
Biomass or wastefired boiler
Sulphur Recirculation
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Ash
Sulphur mass balance
Sulphur in fuel
Flue gas
Sulphur Recirculation
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Sulphur dosage
Ash
Flue gas
Sulphur dosage inhibits corrosion
Sulphur in fuel
Higher SO2 concentration:Alkali chlorides → alkali sulphates(corrosive) (non corrosive)
Sulphur Recirculation
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Ash
Sulphur Recirculation
Sulphur in fuel
Sulphur Recirculation for High Efficiency, Low Corrosion WtE
Sulphur Recirculation
Higher SO2 concentration:Alkali chlorides → alkali sulphates(corrosive) (non corrosive)
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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.
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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.
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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.
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SNCR
Dosage
Oil burn.
Grate
Super-Heaters
Sulphur Recirculation
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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Corrosion probes in the superheater position
(wt%) Cr Ni Mn Si Mo Fe nCr/nFe Add. elements16Mo3 - - 0.6 - 0.3 99.1 0 -
Sanicro 28 27.0 31.0 2.0 0.6 3.5 34.5 0.8 Cu: 1Inconel 625 22.0 58.0 0.5 0.5 9.0 5.0 4.4 -
Air inlet
Air outlet16Mo3, Sanicro28, Inconel625
Wall
450°C
525°C
Sulphur Recirculation
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16Mo3 - Photograph - 525 °C
Reference16Mo3
Sulphur Recirculation16Mo3
Sulphur Recirculation
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Corrosion rate at material temp 450°C (1000 h)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Sanicro 28 Inconel 625 16Mo3
Materialfö
rlust (µ
m/h)
Ref
Recirk
Cor
rosi
onra
te (µ
m/h
)
RefRecirc
Sulphur Recirculation
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Inconel 625 - SEM/EDX images - 450°C
1000 h ReferenceCorrosion attack
1000 h RecirculationUnaffected surface
Beläggning
Deposits
SEM EDX map for chlorine
Deposits
Sulphur Recirculation
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Sanicro 28 - 1000h
1000 h Recirculation1000 h Reference
450°C
525°C
Sulphur Recirculation
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1000 h Corrosion rate measurements
mm/year
Sulphur recirculation enableshigher steam data
Sulphur Recirculation
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Summary
Boiler ash: ESP ash:Less Cl and more SDosage
Furnace
Super-Heaters ESP Eco
SO2-stage
HCl-stage C
onde
nsin
g-sc
rubb
er
Bag houseRe-heat
Stac
kNo detectable acid dew point
Lower high temp corrosion at 450 and 525 ºC material tempLess deposits and particles
1/4 Less dioxins
Emissions unchanged(lower CO and NH3)
Sulphur Recirculation
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NOx primary measure: CUTNOX
Furnace
Primary air
Waste
Bottom ash
Flue gas recirculation
Secondaryair
After Burning Chamber
Grate
CUTNOX: air + water
12 3 4
Lower temp. and increased mixing at λ<1 promote formation of N2 and reduce formation of NO
CUTNOX
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Test at TAMARA: Pilot grate fired furnace (0,5 MWth)0.
187
0.07
7
2.24
0
0.95
0
0.0
0.5
1.0
1.5
2.0
2.5
V7 V8 V9 V10
TOC
(%)
393
341
2429
1713
0
500
1000
1500
2000
2500
3000
V7 V8 V9 V10
Cl (
mg/
kg)
0.37 0.40
76.2
5
36.5
0
0.1
1.0
10.0
100.0
V7 V8 V9 V10
PCD
D/F
TEQ
(ng/
kg)
Less TOC, Cl and PCDD/Fs in the bottom ash
H2O-jet H2O-jet H2O-jet
CUTNOX
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NOx: First commercial CUTNOX at Renova (SE)Preliminary results from CUTNOX ON/OFF tests: Optimisation in progress
NOx mg/Nm3 (dg, 11% O2)
Time
CUTNOX ON OFF ON OFF ON
OFF = 92 (mg/Nm3 d.g.)
ON = 60 (mg/Nm3 d.g.)
Corresponding to34% NOx reduction
CUTNOX
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CUTNOX™ in combination with SNCR
Condensation+ Heat pump
ADIOX®
WESP
Multi-scrubber
NextBAT® flue gas treatment
Dust removalDry/SW/-
reactor
HCl+NH3
SulphurRecirculation SO2MERCOX™+SO2
NextBAT
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SO2
Multi-scrubber
HCl+SO2 removal
Dust removalDry/SW/-
reactor
HCl+NH3
Wet scrubbers yieldextremely low emission values: Insensitive toHCl/SO2 ratio
Waste water free:Dry or semi-wet+ slip scrubber
Cl- + SO42-
to water recipient:Wet scrubber
NextBAT
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CUTNOX™ in combination with SNCR
WESP
NOx + NH3
NH3
SNCR:Lower NOx values calls for increased NH3 dosage and slip
Solution• SCR• SNCR + CUTNOX
NextBAT
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WESP
Dust / fine particles
Dust removal
ProblemPM2.5 in ambient air causes premature death of 350 000 EU citizens per year.
In many urban environments, the ambient air levels of PM2.5 are higher than stipulated by EU directives.
SolutionDust concentrations < 1 mg/Nm3 (10% ofemission limit) can be reached by:
• Bag house filter
• ESP + scrubber integrated WESP
NextBAT
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Dust: Scrubber Integrated WESP
- New scrubber integrated WESP (Wet Electro Static Precipitator) developed by Götaverken Miljö and AWS Corp (IT).
- Fabricated in corrosion resistant conductive FRP
- Cooled condensing collector
• All clean gas dust measurements <0,3 mg/Nm3 dg.• Mean removal efficiency >99%
NextBAT
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PCDD/F removal
Dust removal• Bag house filter + carbon injection
+ ADIOX for Memory Effect minimisation
• ESP + ADIOXADIOX can be incinerated after use –thereby taking dioxins out of the eco-cycle
ADIOX®
NextBAT
Gas Plastic
C
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•
•
•
• ••
•
••
•
••
••
•
•
•
•
•
•
•
•
•
•••
•
•
PCDD/F removal: ADIOX®
- Dioxin absorption in carbon filled polymer- ADIOX material in packings and demisters- If required a separate ADIOX absorber unit
- Always on-line to absorb dioxin- Efficient also during plant start-up
Linköping dry ADIOX absorber
Scrubber interior
ESP+ADIOX
NextBAT
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HgHg° + Hg(II)
using activatedcarbon• Bag house filter + carbon injection
is normally sufficient for Hg removal
• MERCOX in case of very high Hg loads or very low emission values
Hg° using MERCOX
Hg(II) in HCl stage
NextBAT
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Condensation+ Heat pump
Energy recovery
SulphurRecirculation
- Increased energy recovery by some 20-25 % by ocondensation with heat pumps
Vestforbraendingabsorption heat pump
NextBAT
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Energy efficiency: Sulphur Recirculation
SO2
H2SO4
SO2
H2O2
SulphurRecirculation
NextBAT
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Hg: Sakab Hazardous waste incinerator, Sweden
Multifunctional MercOx- and ADIOX scrubberfor Hg°, Hg(ox), HCl, SO2 and dioxin removal
Waste water free!
NextBAT
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Filborna, Helsingborg (SE)
Units Afterboiler
Before scrubber
Emissionguarantee
Emissionexpected
HCl mg/Nm3 2000 45 5 ~ 1SO2 mg/Nm3 1000 50 25 ~ 1HF mg/Nm3 30 1 0.5 ~ 0.1PCDD/Fs ng/Nm3 10 0,05 0,05 ~ 0.02
District heating
AbsorptionHeat pump
SO2 & HF removal
HCl & NH3 removal
Heat recovery
Emissions:
NextBAT
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CUTNOX™ in combination with SNCR
MERCOX™+SO2
Condensation+ Heat pump
ADIOX®
WESP
Multi-scrubber
Dust removalDry/SW/-
reactor
HCl+NH3
SulphurRecirculation
NextBAT
Conclusions
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Conclusions
• Reduced NOx concentration / NH3 consumption
• Less TOC, Cl and PCDD/Fs in the bottom ash
• Smaller variations in temperature and steam flow
CUTNOX
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Conclusions
• Potential for sulphate waste water free operation
• Less dioxins, deposits and ashes
• More electricity production orless corrosion
Sulphur recirculation
Sulphur Recirculation
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