Sulphur Impacts in Coal Fired Sulphur Impacts in Coal Fired p pp pOxyOxy--fuel Combustion with fuel Combustion with

CCSCCSCCSCCS(Impacts and Control Options)(Impacts and Control Options)

Terry WallTerry Wallaa, Rohan Stanger, Rohan Stangeraa*, Joerg Maier*, Joerg Maierbb

a Chemical Engineering University of Newcastle 2308 Australia;a Chemical Engineering University of Newcastle 2308 Australia;a Chemical Engineering, University of Newcastle, 2308, Australia; a Chemical Engineering, University of Newcastle, 2308, Australia; b University of Stuttgart, Germanyb University of Stuttgart, Germany

OutlineOutlineOutlineOutline

General sulphur impactsGeneral sulphur impacts General sulphur impactsGeneral sulphur impacts Pilot WorkPilot Work

S l h Th d iS l h Th d i Sulphur ThermodynamicsSulphur Thermodynamics Control and MitigationControl and Mitigation

The OxyThe Oxy--fuel Processfuel ProcessThe OxyThe Oxy fuel Processfuel ProcessCombustion

Higher H2S & COSSlagging & FoulingSCR – SO3 formation

S C ( ) SO

CO2 ASU

O2

SNCR – (NH4)2SO4

CO2 purity

ESP Sequestration Site

Transport

(Pipeline, Truck, Ship)

Compression

Coal Handlingg

Deep Geological Storage

Recycle

HEX id d i tH2SO4 corrosion

Enhanced – SO3 coating HEX – acid dew pointCooling - H2SO4

pH & porosity

Pilot WorkPilot WorkPilot WorkPilot Work

IHI Test facilityIHI Test facility IHI Test facilityIHI Test facility Callide OxyCallide Oxy--fuel Projectfuel Project

3 l3 l 3 coals3 coals Air & OxyAir & Oxy--fuelfuel Each test ~ 3 hours Each test ~ 3 hours Some work previously reportedSome work previously reported Some work previously reportedSome work previously reported

IHI Pilot PlantIHI Pilot PlantIHI Pilot PlantIHI Pilot PlantOxy-fuel combustion flowchartOxy-fuel combustion flowchartOxy-fuel combustion flowchartOxy-fuel combustion flowchart

Ash Deposits

PAF

Stack

Furnace

Pulverized

Electrical heater

BagGAiRadiativeS i

Sampling positions

PAF

Stack

Furnace

Pulverized

Electrical heater

BagGAiRadiativeS i

Sampling positions

PAF

Stack

Furnace

Pulverized

Electrical heater

BagGAiRadiativeS i

Sampling positions

PAF

Stack

Furnace

Pulverized

Electrical heater

BagGAiRadiativeS i

Sampling positions

SO2/ SO3

Ash Deposits

IDFPulverized

coalBag filterGas

coolerGas

coolerAir

heater

Convective section

Section

Equal velocityaspiration sample

IDFPulverized

coalBag filterGas

coolerGas

coolerAir

heater

Convective section

Section

Equal velocityaspiration sample

IDFPulverized

coalBag filterGas

coolerGas

coolerAir

heater

Convective section

Section

Equal velocityaspiration sample

IDFPulverized

coalBag filterGas

coolerGas

coolerAir

heater

Convective section

Section

Equal velocityaspiration sample

Fl A hFly AshBottom Ash

Air

FDF/GRFElectrical heater

Steam gas heater

Water spray tower O2

Air

FDF/GRFElectrical heater

Steam gas heater

Water spray tower O2

Air

FDF/GRFElectrical heater

Steam gas heater

Water spray tower O2

Air

FDF/GRFElectrical heater

Steam gas heater

Water spray tower O2

Pilot SOPilot SO22 ResultsResults

400

5002000

x3 higher

300

SO2,

m

g/M

J

1000

1500

O2,

(d

ry)

100

200

S m

500

SO

ppm

25 30% l0

0 0.2 0.4 0.6 0.8 1Fuel-S, %

00 0.2 0.4 0.6 0.8 1

Fuel-S, %

25-30% less

Oxy-fuel concentration higher but produces LESS total SO2

Higher concentration acts as driver for secondary products

Pilot SO3 ResultsPilot SO3 ResultsPilot SO3 ResultsPilot SO3 Results

15

20

150

160

170

o C

Measured Oxy FiredOxy Fired

10

SO

3,

ppm

(dry

)

130

140

150

d D

ew P

oint

,

Air Fired

0

5

0 0 2 0 4 0 6 0 8 1100

110

120

0 0 2 0 4 0 6 0 8 1A

cid

Measured Air Fired

0 0.2 0.4 0.6 0.8 1

Fuel-S, %0 0.2 0.4 0.6 0.8 1

Fuel-S, %

Pilot Ash ResultsPilot Ash ResultsPilot Ash ResultsPilot Ash Results

1 2

Fly Ash

1

1.2

AirO

1

1.2

Air Fired

Oxy FiredCoal C

0.6

0.8

1

SO3,

%

Oxy

Coal C 0.6

0.8

S as

SO

3,

% (a

d)

0.2

0.4S as

0.2

0.4

S0

0 0.2 0.4 0.6 0.8 1

Fuel-S, %

0Bottom Ash Fly Ash Deposit

RadiativeDeposit

Convective

No SO3 in Bottom Ash and Radiative Deposits for other coals

Mass BalanceMass Balance&&

ThermodynamicsThermodynamicsThermodynamicsThermodynamics

Theoretical Mass BalanceTheoretical Mass BalanceTheoretical Mass BalanceTheoretical Mass Balance

3000

4000

Measured Air

Measured OxyDifference due

2000

3000

SO2,

m

(dry

)

Difference due to the formation

of secondary sulphur

1000

pp

pproducts

00 0.2 0.4 0.6 0.8 1

F l S %Fuel-S, %

Theoretical Mass BalanceTheoretical Mass BalanceTheoretical Mass BalanceTheoretical Mass Balance4000

O h t l

3000

ppm

Oxy - hot recycle

Oxy - recycle after NOx,SOx, H2O removed

Air Fired

2000

tical

SO

2,

Effect of Recycle

1000

Theo

ret Recycle

00 0.2 0.4 0.6 0.8 1

Fuel-S, %

Effect of Lower Flow Rate

Fuel S, %

InIn--flame Sulphur Productsflame Sulphur ProductsInIn flame Sulphur Productsflame Sulphur Products(Coal A Thermodynamics at 1500C)

14 14

10

12

14

io

10

12

14

tio

H2S

SO3

4

6

8

Oxy

/Air

otal

Mol

ar R

ati

COSSO3

4

6

8

Oxy

/Air

otal

Mol

ar R

a t

SO

COS

0

2

4T

SO2 H2S

0

2

4T SO2

WITH RECYCLEONCE THROUGH

0.7 0.8 0.9 1.0 1.1 1.2 1.3

Equivalence Ratio

0.7 0.8 0.9 1.0 1.1 1.2 1.3

Equivalence Ratio

WITH RECYCLE

(~69% recycle, 28% O2 IN, 5% O2 OUT)

ONCE THROUGH

(O2/CO2 vs O2/N2)

SOSO22 Conversion to SOConversion to SO33

3030

SOSO22 Conversion to SOConversion to SO33

20

25

%

OXY -

AIR -

Fuel-S Air Oxy%, db ppm ppm

Coal A 0.24 2 7Coal B 0.57 9 18Coal C 0.88 3 11

SO3

25

30

%

OXY -

AIR

Fuel-S Air Oxy%, db ppm ppm

Coal A 0.24 2 7Coal B 0.57 9 18Coal C 0.88 3 11

SO3

15

20

SO2

SO

3 nv

ersi

on, % AIR -

15

20

O2

SO

3 nv

ersi

on, % AIR -

IVD Pilot- 0.5 MWt

(Maier et al )

1000C used to estimate SO3 conversion for

IVD Pilot 0.5 MWt

(Maier et al)

5

10SC

on

IHI Pilot- 1.2 MWt

(this study)5

10SC

o n

IHI Pilot- 1.2 MWt

(this study)

acid dew point

(Okkes, Verhoff & Banchero

( )

00 500 1000 1500

Temperature, C1200

00 500 1000 1500

Temperature, C1200

methods)

Mitigation OptionsMitigation OptionsMitigation OptionsMitigation Options

Air Separation

Unit

O2

N2

Soot Blowing

ESPSequestration Coal

N2

CO2compression

Low S Coal

Sulphur S bbESP SiteTransport

(pipeline, truck, etc)Handling

Limestone

Scrubber

Condenser/

Sulphur removal in compression circuit

Deep Geological Storage

Recycled Flue Gas Sulphur Scrubber

Condenser/ Cooler

Control StrategiesControl StrategiesControl StrategiesControl Strategies SO2 limited SO2 limited -- low sulphur coals low sulphur coals

SO2 removed SO2 removed -- FGD (85FGD (85--98% capture)98% capture)Limestone addition (<50% capture)Limestone addition (<50% capture)Limestone addition ( 50% capture)Limestone addition ( 50% capture)High calcium coals (5High calcium coals (5--10% capture)10% capture)Cooling/Caustic wash (Air Liquide)Cooling/Caustic wash (Air Liquide)In compression (Air Products)In compression (Air Products)In compression (Air Products)In compression (Air Products)In purificationIn purification

SootSoot--blowersblowers Flue Gas above acid dew pointFlue Gas above acid dew point Corrosion resistant materialsCorrosion resistant materials Corrosion resistant materialsCorrosion resistant materials

ConclusionConclusion –– Pilot SulphurPilot SulphurConclusion Conclusion Pilot SulphurPilot Sulphur

Higher SO2 in OxyHigher SO2 in Oxy--fuelfuel Higher SO2 in OxyHigher SO2 in Oxy fuelfuel Higher SO3 & acid dew pointHigher SO3 & acid dew point

Fl A h & B tt A h ff t dFl A h & B tt A h ff t d Fly Ash & Bottom Ash unaffectedFly Ash & Bottom Ash unaffected OxyOxy--fuel Deposits higher in Sfuel Deposits higher in S

ConclusionConclusion-- Sulphur ImpactsSulphur ImpactsConclusionConclusion Sulphur ImpactsSulphur Impacts

Sulphur Impacts throughout oxySulphur Impacts throughout oxy--fuel CCSfuel CCS Sulphur Impacts throughout oxySulphur Impacts throughout oxy fuel CCSfuel CCS OxyOxy--fuel SOfuel SO22 -- higher conc, lower outputhigher conc, lower output

SOSO C t ti d i f S d tC t ti d i f S d t SOSO22 Concentration driver for S productsConcentration driver for S products Furnace Products different with recycleFurnace Products different with recycle SOSO33 conversion ~thermodynamics 1000conversion ~thermodynamics 1000CC

Thank you for your attentionThank you for your attention

Sulphur ImpactsSulphur ImpactsSulphur ImpactsSulphur ImpactsFurnaceFurnace corrosion, slaggingcorrosion, slaggingFurnaceFurnace corrosion, slaggingcorrosion, slagging

Convective PassConvective Pass corrosion, foulingcorrosion, foulingSCRSCR fouling, catalytic formationfouling, catalytic formation-- SOSO33g, yg, y 33

ESPESP higher performancehigher performanceHeat ExchangeHeat Exchange acid dew pointacid dew pointCompressionCompression HH22SOSO44

COCO22 PurityPurity SOSO22

TransportTransport corrosion, Hcorrosion, H22SOSO44

StorageStorage Corrosion, injection (pH zone)Corrosion, injection (pH zone)

InIn--flame Sulphur Productsflame Sulphur ProductsInIn flame Sulphur Productsflame Sulphur Products(Thermodynamics at 1500C)

8

9

10

8

9

10

o

5

6

7

XY/A

IR

ntra

tion

ratio

SO3COS

4

5

6

7

OXY

/AIR

nt

ratio

n R

atio

COS

H2SSO3

1

2

3

4OC

once

n

SO2

H2S1

2

3

4OC

once

n

SO2

00.8 0.9 1 1.1 1.2

Equivalence Ratio

H2S0

0.8 0.9 1 1.1 1.2

Equivalence Ratio

WITH RECYCLE

(~69% recycle, 28% O2 IN, 5% O2 OUT)

ONCE THROUGH

(O2/CO2 vs O2/N2)

SOSO22 in Compressionin CompressionLow H2O Scenario – 50ppmHigh H2O Scenario – 500ppm

For Aquifer Storage - 3% O2, 100ppm SO2, 50ppm H2O, CO2 balanceFor EOR Storage - 100ppm O2, 100ppm SO2, 500ppm H2O, CO2 balance

(Dynamis Project recommendations for Pre-combustion capture)

IVDIVD -- StuttgartStuttgartIVD IVD StuttgartStuttgart

6000 30

SO2 H2S SO2+H2S O2

6000 30(SO +H S)max

4000

ppm

]

18

24

%]

4000

ppm

]

18

24

%]

(SO2+H2S)max

2000SO2,

H2S

[p

6

12

18

O2 [

vol%

2000SO

2, H

2S [p

6

12

18

O2 [

vol%

(SO2+H2S)max

AIR-BLOWN COMBUSTION_LAUSITZ OF27_3000 COMBUSTION_LAUSITZ

00 0.5 1 1.5 2 2.5

Distance from Burner [m]

0

6

00 0.5 1 1.5 2 2.5

Distance from Burner [m]

0

6(SO2+H2S)max

Distance from Burner [m] Distance from Burner [m]

Sulphur Products & EffectsSulphur Products & Effects

In-flameAcid dew point

C i i

Convective Fouling

1.0

H SO

Cooling Flue GasIn flame reduction products

Corrosion in compression

0.8

ium

SO2H2SO4

SO3

0 3

0.5

Equi

libri

0.0

0.3

0 500 1000 15000 500 1000 1500

Temperature,oC

Limestone AdditionLimestone AdditionLimestone AdditionLimestone AdditionC

erat

ure,

C

Tem

pe

SO2, ppm

* Assumes max Ca/S = 2

Limestone AdditionLimestone AdditionLimestone AdditionLimestone Addition

* Assumes max Ca/S = 2