Czestochowa University of TechnologyPoland

Turow Power Plant S.A.

Sulfur capture in Sulfur capture in a 235 MWa 235 MWCFB CFB boiler boiler by by mechanicalmechanical

activation of sorbentsactivation of sorbents

Prof. Wojciech NOWAKProf. Wojciech NOWAK

47th IEA Meeting, Złotniki Lubańskie, 2003

BełchatówKozieniceTurówPołaniecDolna OdraPątnówRybnikJaworzno IIIŁaziskaŁagiszaOpole*SierszaAdamówOstrołękaSkawinaKoninJaworznoStalowa WolaBlachowniaHalembaPomorzanyMiechowiceSzombierki

BełchatówKozieniceTurówPołaniecDolna OdraPątnówRybnikJaworzno IIIŁaziskaŁagiszaOpole*SierszaAdamówOstrołękaSkawinaKoninJaworznoStalowa WolaBlachowniaHalembaPomorzanyMiechowiceSzombierki

432026402036174016741600160011901040769720705600600535478443357244200112101

44

432026402036174016741600160011901040769720705600600535478443357244200112101

44*/ docelowa – 2160 MW*/ docelowa – 2160 MW

ELEKTROWNIE:ELEKTROWNIE:moc

osiągalna(MW):

mocosiągalna

(MW):

1.2.3.4.5.6.7.8.9.

10.11.12.13.14.15.16.17.18.19.20.21.22.23.

1.2.3.4.5.6.7.8.9.

10.11.12.13.14.15.16.17.18.19.20.21.22.23.

21

5

6

16

14

13

12

3

4

181122 23 10

172019

7 9 8 1215

Polish utility power plants

Turow Power Plant

Power Plant Capacity [MW]`̀

PolishPolish CFBCFB power dimensionpower dimension

Largest Largest CFB market CFB market in Europein EuropePionier Pionier in supercritical in supercritical OTH CFB OTH CFB boilerboilerExtensive experience and knowledgeExtensive experience and knowledgeWide range of fuelsWide range of fuelsCofiring coal with slurryCofiring coal with slurry, , biomassbiomass, , animal animal wasteswastesVery good emission performance Very good emission performance Ambitious programs undertaken Ambitious programs undertaken by by power power plants and universitiesplants and universitiesCFB CFB biomassbiomass/ / waste gasificationwaste gasification –– new new challengechallenge

OWNER/LOCATIONOWNER/LOCATION YEARYEAR TYPETYPE CAPACITYCAPACITY FUELSFUELS

Turow Power Plant S.A.Turow Power Plant S.A. 19981998 CFBC Unit 1 and 2CFBC Unit 1 and 2Hot cyclonesHot cyclones 2 x 235 MWe2 x 235 MWe Brown coal, LigniteBrown coal, Lignite

Turow Power Plant S.A.Turow Power Plant S.A. 20002000 CFBC Unit 3CFBC Unit 3Hot cyclonesHot cyclones 235 MWe235 MWe Brown coal, LigniteBrown coal, Lignite

Turow Power Plant S.A.Turow Power Plant S.A. 20022002--20042004 CFBC Units 4, 5 & 6CFBC Units 4, 5 & 6Hot cyclonesHot cyclones 3 x 260 MWe3 x 260 MWe Brown coal, LigniteBrown coal, Lignite

EC Katowice S.A.EC Katowice S.A. 20002000 CFBC CFBC SteamSteam--cooled cyclonecooled cyclone 120 MWe120 MWe Bituminous coal,Bituminous coal,

coal slurrycoal slurryPower Plant PSEPower Plant PSEJaworzno II S.A.Jaworzno II S.A. 19991999 CFBC Units 1 & 2CFBC Units 1 & 2

Compact CFBCompact CFB 2 x 70 MWe2 x 70 MWe Bituminous coal,Bituminous coal,coal slurrycoal slurry

EC Chorzow ElchoEC Chorzow Elcho 20032003 CFBC Units 1 & 2CFBC Units 1 & 2Compact CFBCompact CFB 2 x 113 MWe2 x 113 MWe Bituminous coalBituminous coal

EC Zeran, WarsawEC Zeran, Warsaw 19971997 CFBC Unit ACFBC Unit AHot cyclonesHot cyclones 315 MWe315 MWe Bituminous coalBituminous coal

EC Zeran, WarsawEC Zeran, Warsaw 20012001 CFBC Unit BCFBC Unit BSteamSteam--cooled cyclonecooled cyclone 315 MWe315 MWe Bituminous coalBituminous coal

EC BielskoEC Bielsko--BialaBiala 19971997 CFBC CFBC Hot cyclonesHot cyclones 177/165 MWe177/165 MWe Bituminous coalBituminous coal

Polpharma Polpharma Starogard GdańskiStarogard Gdański 19931993 CFBC CFBC

Hot cyclonesHot cyclones 2 x 60.2 MWe2 x 60.2 MWe Bituminous coalBituminous coal

EECC TychyTychy 19991999 CFBC CymicCFBC CymicInternal cycloneInternal cyclone

37 MWth electricity37 MWth electricity70 MWth dictric heat70 MWth dictric heat Bituminous coalBituminous coal

EC OstrolekaEC Ostroleka 19971997 BFBC BFBC bubbling typebubbling type 30 MWth30 MWth Bark, paper wasteBark, paper waste

EC SierszaEC Siersza 2001, 20032001, 2003 CFBC Units 1 & 2CFBC Units 1 & 2Hot cyclonesHot cyclones 2 x 338.5 MWth2 x 338.5 MWth Bituminous coalBituminous coal

UNITS 4-6 CFB COMPACT IN ELEKTROWNIA TURÓW

Capacity 260 MWeSteam pressure 16.7 MPaSteam temperature 565 oCEfficiency (netto) 39.1%

Superheater INTREX

Comparison of parameters for CFB boilers (235-260 MWe) and 460 MWe CFB

Specification Blocks with cyclones

CFB Turow No 1,2,3

Blocks 4-6 Compact type

Turow

Block 460 MW PKE S.A. Lagisza

Electric capacity, gross, MWe 235 262 460 Live steam flow, kg/s 185.4 200 359.8 Live steam pressure at turbine inlet, MPa

13.17 16.65 27.5

Live steam temperature at turbine inlet, oC

540 565 560 (+5/0)

RH steam temperature, oC 540 565 580 RH steam flow, kg/s 165.5 182 313.1 Cold reheat steam pressure, Mpa 2.8 4.2 5.3 Cold reheat steam temperature, oC 312 350 310.5 RH steam pressure at turbine inlet, MPa

2.5 3.8 4.88

Feed water temperature, oC 242.6 250 290 Flue gases outlet temperature, oC 157 138 122

460 MWe CFBEfficiency (brutto) 47%

Experience Experience

in in thethe fieldfield ofof utilization utilization

ofof activatedactivated fly ash and sorbentsfly ash and sorbents

in in SOSO22 capture in capture in

largelarge--scale scale CFBCFB boilersboilers

S < 0.35S < 0.35

S > 0.55S > 0.55

High sorbent consumption required to meet environmental standardsHigh sorbent consumption required to meet environmental standards

00 11 22 33 44 55 66 77 88 99 1010 1111 1212 1313 1414 1515 161600

1010

2020

3030

4040

5050

6060

7070

8080

9090

100100

110110

Ca/S molar ratioCa/S molar ratio

Higher operation costsHigher NOx level

Loss of combustion efficiencyIncreased ash disposal costs

Higher operation costsHigher NOx level

Loss of combustion efficiencyIncreased ash disposal costs

Higher Ca/S ratioHigher Ca/S ratio

The following factors have their impact on obtaining higher levels of desulfurization efficiency:The following factors have their impact on obtaining higher levels of desulfurization efficiency:

sorbent’s granulation,sorbent’s granulation,

sorbent’s surface,sorbent’s surface,

amount of the active content,amount of the active content,

amount of inserted sorbent (mole ratio: Ca/S), amount of inserted sorbent (mole ratio: Ca/S),

time residence by sorbent in contact with combustion gas in a combustion chambertime residence by sorbent in contact with combustion gas in a combustion chamber

homogeneity of sorbent-combustion gas intermixity homogeneity of sorbent-combustion gas intermixity

DEVELOPMENT OF HIGH-REACTIVITY SORBENTS

Reactivity of the sorbent particles Reactivity of the sorbent particles is an important parameter which is an important parameter which dictates the effectiveness of sulfur dictates the effectiveness of sulfur capture in CFB boilers, similar to capture in CFB boilers, similar to the other combustion technologiesthe other combustion technologies

SCHEMAT OF MODIFIEDSCHEMAT OF MODIFIEDSCHEMAT OF MODIFIED SORBENT PRODUCTIONSORBENT PRODUCTIONSORBENT PRODUCTION

WODA

WTRYSKSORBENTU

PYŁWĘGLOWY

Z MŁYNA Z ESP

MIESZALNIK

ZBIORNIK SORBENTU LUB

SPOIWA SUCHEGO

ELEKTROFILTR

KOCIOŁ

REAKTOR OBROTOWY

CaO POPIÓŁ

CHEMICAL ACTIVATION MECHANICAL ACTIVATION

Mechanical ActivationMechanical Activation

Patent Patent numbernumber 180380 180380 coverscovers thethe technology technology andandinstalationinstalation for for obtainingobtainingsettingssettings materialsmaterials fromfrom CFB CFB and and PCPC boilersboilers

PRINCIPLE OF MECHANICAL ACTIVATION

particle before activation

activation particle after activation

Activated particle after calcination

New pores after activation

Existing pores enlarged after

activation

Activated particle after sulfation

1 10 1000,00

0,02

0,04

0,06

0,08

0,10

0,12

0,14

0,16

0,18

0,20

1 10 1000,00

0,02

0,04

0,06

0,08

0,10

0,12

0,14

0,16

0,18

0,20

sorbent bez aktywacji

pow

ierz

chni

a w

lasc

iwa

poro

w [m

2 /g]

srednia srednica porow - d [nm]

sorbent aktywowany

pow

ierz

chni

a w

lasc

iwa

poro

w [m

2 /g]

SURFACE AREA OF PORES

particle before activation

Activated particle

Activated \Non activated

0,01 0,10

20

40

60

80

100

Cum

ulat

ive

dist

ribut

ion

[%]

sieve size [mm]

No activated Activation

1600 rpm 2400 rpm 2800 rpm

Addition of fluidized bed ashes to sorbent

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

+

++++

+++++

_++++__

+_+_

++_

___

+++++

+++++

___

++++++++ ++___ _

___

___++++

+

Sorbent particles on fly ash surface

CaO particles inCFB fly ashes

Results of mechanical Results of mechanical activationactivation

Larger specific surface areaLarger specific surface areaShifting pore volume distribution Shifting pore volume distribution to to smaller smaller poresporesIncreasing gel pores Increasing gel pores (<10 (<10 nmnm))Formation of defectsFormation of defectsFragmentation of aglomeratesFragmentation of aglomeratesDesintagration of metakaloiniteDesintagration of metakaloiniteSpheroidizingSpheroidizing CFB CFB ash particlesash particlesSeparation of activated material from Separation of activated material from unactivated due unactivated due to to electrostatic electrostatic charge on charge on the surfacethe surface

Activator elements Activator elements capacitycapacity 3 t/h 3 t/h

RotorFrame cover

Activatingchamber

CFB CFB ash utilizationash utilization: pilot plant : pilot plant at Turow Power at Turow Power PlantPlant

Mechanical activation

MOVEMENT OF ACTIVATED PARTICLES

ActivatorActivator 5 t/h 5 t/h

Activator

Control panel

Loading sleeve

TECHNICAL UNIVERSITY OF CZESTOCHOWADEPARTMENT OF HEATING,

VENTILATION AND AIR PROTECTION

TECHNICAL UNIVERSITYOF CZĘSTOCHOW A

ENERGY ENGINEERINGLABORATORY

Reactivity Index and Sorption

Reactivity test RI CI excellent < 2,5 > 120 very good 2,5 - 3,0 100 -120

good 3,0 - 4,0 80 - 100 sufficient 4,0 - 5,0 60 - 80

low quality > 5,0 < 60

Determination of the limestone reactivity should be somehow standardized and more uniform for all CFB boilers

Determination of the limestone reactivity should be somehow standardized and more uniform for all CFB boilers

RI stands for Ca/S molar ratio, which shows the amount of Ca before the test, and the amount of sulphur after. CI is defined as amount of sulphur (in grams), absorbed by kilogram of tested calcium

RI stands for Ca/S molar ratio, which shows the amount of Ca before the test, and the amount of sulphur after. CI is defined as amount of sulphur (in grams), absorbed by kilogram of tested calcium

TECHNICAL UNIVERSITY OF CZESTOCHOWADEPARTMENT OF HEATING,

VENTILATION AND AIR PROTECTION

TECHNICAL UNIVERSITYOF CZĘSTOCHOW A

ENERGY ENGINEERINGLABORATORY

Test unit

2,64

2,21

1,92 1,86

2,13 2,1

2,32,43 2,45 2,45

2,78

1,98

0,00

0,50

1,00

1,50

2,00

2,50

3,00

węg

lan

wap

nia

bez

akty

wac

ji

węg

lan

wap

nia

zak

tyw

acją

popi

ół +

20%

CaC

O3

z ak

tyw

acją

popi

ół +

40%

CaC

O3

z ak

tyw

acją

popi

ół +

60%

CaC

O3

z ak

tyw

acją

sorb

ent z

pop

iołu

fluid

alne

go b

ezdo

datk

u

sorb

ent z

pop

iołu

fluid

alne

go +

15%

CaO

sorb

ent z

pop

iołu

fluid

alne

go +

22,5

%C

aO

sorb

ent z

pop

iołu

fluid

alne

go +

30%

CaO

sorb

ent z

pop

iołu

fluid

alne

go +

37,5

%C

aO

rodzaj sorbentu

wsk

aźni

k re

akty

wno

ści R

I

REACTIVITY INDEX

MECHANICALACTIVATION

CHEMICALACTIVATIONCaCO3

activatedCaCO3

Conversion`̀

Without activation

limestone

Mechanicalactivation

limestone

limestone+ fly ash

Chemicalactivation

limestone+ fly ash

0 1 2 3 4 5 6 7 8 9 10

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

Con

vers

ion

X [-]

Sorbent

limestonelimestonefly ash + 20%

limestone

fly ash + 20%

limestone

fly ash + 40%

limestone

fly ash + 40%

limestone

fly ash + 60%

limestone

fly ash + 60%

limestonefly ash fly ash fly ash

+ 15%lime

fly ash + 15%lime

fly ash + 22.5%

lime

fly ash + 22.5%

lime

fly ash + 30%lime

fly ash + 30%lime

fly ash + 37.5%

lime

fly ash + 37.5%

limelimestonelimestone

Size [µm]10 100 1000 10000

Per c

ent p

assi

ng

1

2

5

10

20

30

40

50

60

70

80

90

95

98

99

FW requirement

Actual sizedistribution

Since the limestone size dis-tribution has a very impor-tant influence on the desul-furization efficiency, it has to be as close to the provided by supplier curves as possi-ble. In our opinion the requ-ired characteristic is too res-trictive and mill producers are not able to comply with such requirements in the full range.

Since the limestone size dis-tribution has a very impor-tant influence on the desul-furization efficiency, it has to be as close to the provided by supplier curves as possi-ble. In our opinion the requ-ired characteristic is too res-trictive and mill producers are not able to comply with such requirements in the full range.

LIMESTONE EFFICIENCY CONVERSION

4 8 12 16 20 25

0

10

20

30

40

50

Kon

wer

sja

Ca

w

[%]

Uziarnienie CaCO3 w [µm]

Conversion is improved when size of the limestone particles is reduced – a process that takes place naturally in the CFB boiler

Cyclone Cyclone inlet inlet modificationmodification

Solids concentrationSolids concentrationBefore modification After modification

Cyclone Cyclone inletinlet

0,01 0,1 1 100

200

400

600

800

1000

1200Material recyrkulowany

- cyklon po modernizacji - cyklon przed modernizacja

dp [mm]

mre

c [kg

/s]

After modernizationBefore modernization

Pilot plant Pilot plant installation at the Turow Power installation at the Turow Power PlantPlant

LEGENDA1. Silo for limestone’s powder2. Silo for ash3. Aeration guter-pipe4. Silo for mixture of limestone and

ash5. Activator

wdmuch sorbentu do kotła

transport sorbentu

Sorbent Sorbent activation in activation in a 235 MW CFB a 235 MW CFB boiler at Turow Power boiler at Turow Power PlantPlant

Fly ash 60%Sorbent 40%

InstallationInstallation for for productionproduction ofofhighhigh--reactivereactive sorbentssorbents

Performance testsPerformance tests

Stable boiler operationStable boiler operation

26% sorbent 26% sorbent consumption reduction at consumption reduction at 100% MCR 100% MCR and and 26.3% 26.3% at at 80% MCR80% MCR

99.2% 99.2% availabilityavailability

Lower Lower SOSO22 and NOand NOxx