Antonio Coppola, Fabio Montagnaro, Piero Salatino ...Antonio Coppola, Fabio Montagnaro, Piero...

Antonio Coppola, Fabio Montagnaro,Piero Salatino, Fabrizio Scala

Istituto diRicerchesulla Combustione ‐CNR

Università degli Studi diNapoliFedericoII

Cal‐Mod Project

5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom

Modelling and experimental validation of Calcium Looping CO2-capture process for near-zero CO2 emission power plants (2010-2014)

Cal‐Mod Project


Work Package 0 – Project ManagementWP-Leader:USTUTT

Work Package 1Optimisation of Calcium Looping process by improving limestone

utilisationWP-Leader: IRC

Partners: WUT, TITAN; EnBW, ENEL

Work Package 2Development and validation of CFD

reactor modelsWP-Leader: CERTH/ISFTAPartners: USTUTT, ENEL

Work Package 3Development of process model for

designing demostration plantsWP-Leader: EnBW

Partners: USTUTT, CERTH/ISFTA, ENEL

Work Package 4Feasibility analisys of lime-based CO2

capture processWP-Leader: ENEL

Partners: USTUTT, TITAN, CERTH/ISFTA, EnBW

Experimentaldata & experience

Kinetic and attrition data

Reactordesign data

Experimentaldata

Delivery of purge samples

Reactor design data

Design rules for scale-up / Process requirements

Shimizuetal.,1999,2002

Calcium‐LoopingCalcium‐Loopingis apost‐combustion technology which uses limetocapture

carbondioxide fromfluegas


Main Issues

Cycle #

2 4 6 8 10 12 14

Cap

ture

Cap

acity

DecayofCO2 CaptureCapacityofthesorbent

Sintering

Temperature,duration ofcalcination,impurities andreaction environment

(CO2,H2O)

Change ofpore size


Main Issues

Cycle #

2 4 6 8 10 12 14

Cap

ture

Cap

acity


SinteringPresenceofSO2

CaO +SO2 +½O2→CaSO4


Main Issues

Cycle #

2 4 6 8 10 12 14

Cap

ture

Cap

acity


Sintering

PresenceofSO2

CaO +SO2 +½O2→CaSO4• Externalsulfatelayer• Changeofmechanicalproperty

• Permanentlossofthesorbent

StanmoreandGilot,2005;Blameyetal.,2010;Montagnaroetal.,2010


Main Issues

circulationofthesolidphasebetweenthereactors

intimatecontactbetweenthesolidandgasphases

CO2 recycledfromtheoutletgas,oraCO2/H2Omixture

comingfromthecombustionprocess

Two Interconnected Fluidized Beds


Main Issues

Two Interconnected Fluidized Beds

Attrition/FragmentationPhenomena

PrimaryFragmentation

SecondaryFragmentation

AttritionbyAbrasion

Few dataonattrition ofsorbent duringcarbonation/calcination cycles areavailable inthe

literature (Blamey etal.,2010)


tocomparetheperformanceofdifferentsorbentsunderrealisticconditions(calcinationunderoxy‐firingconditions)

CO2 CaptureCapacity

attrition/fragmentationphenomena

theeffectofthepresenceofSO2

testswithoutSO2 havebeencarriedoutforcomparison

Aims

Fivecalcination/carbonationcycles

20goffreshsorbent(0.4‐0.6mm)

150gofsilicasand(0.85‐1.0mm)

U=0.7m/s(calcination)‐ 0.6m/s(carbonation)

thedurationofeachstagewassuchthatcalcination/carbonationwascomplete

EvaluationofPSD(bysieving)

Evaluationoffinesgeneration(bymeansoffilters)

Experimental apparatus andprocedures

thermocouple

gaspreheater

ovens

•ID:40mm•H:1320mm

filters(=1ford>10μm

hopper


Experimental conditions

Calcination/Carbonation

WithoutSO2NoSO2

WithSO2intermediateconditions

WithSO2severeconditions

Duration[min] 20/15Temperature[°C] 940/650InletCO2 [%v/v] 70/15InletSO2 [ppmv] 0/0 750/75 1500/1500


Time, s

0 500 1000 1500

CO

2, %

v/v

69.5

70.0

70.5

71.0

71.5

T = 930°CT = 940°C

Inlet concentration

Experimental conditions

Calcination/Carbonation

WithoutSO2NoSO2

WithSO2intermediateconditions

WithSO2severeconditions

Duration[min] 20/15Temperature[°C] 940/650InletCO2 [%v/v] 70/15InletSO2 [ppmv] 0/0 750/75 1500/1500

Materials

Sample OriginMassicci Italy

Schwabian Alb GermanyEnBW Germany

Xirorema Sand GreeceTarnow Opolski PolandCzatkowice Poland

Redziny Dolomite Poland


No SO2

Cycle, #

1 2 3 4 5

Cap

ture

Cap

acity

[gC

O2/in

itial

gso

rben

t]

0.00

0.05

0.10

0.15

0.20

0.25MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny dolomite

Severe Conditions

Cycle, #

1 2 3 4 50.00

0.05

0.10

0.15

0.20


Results:CO2 CaptureCapacity‐ CC

0.02‐0.07gCO2/gSorbent 0.1‐0.2gCO2/gCaCO3Undermilder conditionsBlamey et al.,2010

0.12gCO2/gSorbent

Sintering resistance


No SO2

Cycle, #

1 2 3 4 5

Cap

ture

Cap

acity

[gC

O2/in

itial

gso

rben

t]

0.00

0.05

0.10

0.15

0.20


Severe Conditions

Cycle, #

1 2 3 4 50.00

0.05

0.10

0.15

0.20



0.02‐0.07gCO2/gSorbent 0.1‐0.2gCO2/gCaCO3Undermilder conditionsBlamey et al.,2010

0.12gCO2/gSorbent Sintering resistance

0.004‐0.02gCO2/gSorbent

0.037gCO2/gSorbent

SO2=1500ppm



Intermediate Conditions

Cycle, #

1 2 3 4 50.00

0.05

0.10

0.15

0.20


No SO2

Cycle, #

1 2 3 4 5

Cap

ture

Cap

acity

[gC

O2/in

itial

gso

rben

t]

0.00

0.05

0.10

0.15

0.20



SO2=750/75ppm

0.02‐0.07gCO2/gSorbent 0.02‐0.04gCO2/gSorbentPrevalence ofSintering

0.12gCO2/gSorbent 0.06gCO2/gSorbent

No SO2

d [m]

0 100 200 300 400 500

Cum

ulat

ive

PSD

#

0.0

0.2

0.4

0.6

0.8

1.0

MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny


d [m]

0 100 200 300 400 5000.0

0.2

0.4

0.6

0.8

1.0Severe Conditions

d [m]

0 100 200 300 400 5000.0

0.2

0.4

0.6

0.8

1.0

Results:Particle Size Distribution– PSD(After the5th carbonation)


initial size range:400‐600μm

SO2=750/75ppm SO2=1500ppm

similar shape andlimited fragmentation

SO2 slightlyreducestheextentoffragmentation

LIMESTONESLIMESTONES

No SO2

d [m]

0 100 200 300 400 500

Cum

ulat

ive

PSD

#

0.0

0.2

0.4

0.6

0.8

1.0

MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny


d [m]

0 100 200 300 400 5000.0

0.2

0.4

0.6

0.8

1.0Severe Conditions

d [m]

0 100 200 300 400 5000.0

0.2

0.4

0.6

0.8

1.0

Results:Particle Size Distribution– PSD(After the5th carbonation)


SO2=750/75ppm SO2=1500ppm

extensive particle fragmentation

SO2 slightlyreducestheextentoffragmentation

DOLOMITEDOLOMITE

initial size range:400‐600μm

Limestones%

Sor

bent

loss

[% g

elut

riate

d/in

itial

gso

rben

t]

0.0

0.2

0.4

0.6

0.8

1.0CalcinationCarbonation

Cycle, #1 2 3 4 5

0.0

0.2

0.4

0.6

0.8

1.00.0

0.2

0.4

0.6

0.8

1.0

No SO2

Severe Conditions


Results:Average Elutriation Loss


at low SO2 concentrations theaverage elutriation loss slightly

increases

at highSO2 concentrations theaverage elutriation loss slightly

decreases

SO2=1500ppm

SO2=750/75ppm

elutriation loss is approximatelythesame during thecalcination and

thecarbonation stages

‘Limestones’referstotheaveragevaluesofthesixlimestones

Limestones%

Sor

bent

loss

[% g

elut

riate

d/in

itial

gso

rben

t]

0

1

2

3

4

5CalcinationCarbonation

Redziny dolomite

0

1

2

3

4


Cycle, #1 2 3 4 5

0

1

2

3

4

5

Cycle, #1 2 3 4 5

0

1

2

3

4

5

No SO2No SO2

Severe Conditions Severe Conditions

0

1

2

3

4

5

0

1

2

3

4

5Intermediate Conditions Intermediate Conditions



thedolomiteabrasion is muchhigher than limestone

thepresence ofSO2 slightlydecreases theaverage

elutriation loss


SO2=1500ppm

SO2=750/75ppm

Limestones%

Sor

bent

loss

[% g

elut

riate

d/in

itial

gso

rben

t]

0

1

2

3

4


Redziny dolomite

0

1

2

3

4


Cycle, #1 2 3 4 5

0

1

2

3

4

5

Cycle, #1 2 3 4 5

0

1

2

3

4

5

No SO2No SO2

Severe Conditions Severe Conditions

0

1

2

3

4

5

0

1

2

3

4

5Intermediate Conditions Intermediate Conditions



0.19%

0.23%

0.10%

0.39%

0.23%

0.33%


Conclusions


CO2 capture Attrition

Oxi‐firingconditions: strongnegativeeffect positiveeffect

Effect ofSO2 negativeeffect slighteffect

LimestonevsDolomite dolomite limestone

theaveragelimestonelossratebyelutriationisabout0.5%/h

Conclusions


Oxi‐firing conditions:

CO2 capture:negative

Attrition:positive

Effect ofSO2:

CO2 capture:detrimental but manageable

Attrition:slight effect

LimestonevsDolomite:

CO2 capture:Dolomite

Attrition:Limstone

Calcium‐Looping

+SO2

CaO(s) +SO2(g)+½O2(g)→CaSO4(s) CaO(s) +SO2(g) +½O2(g)→CaSO4(s)

Fromburning oftheauxiliary fuel


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Antonio Coppola, Fabio Montagnaro, Piero Salatino ...Antonio Coppola, Fabio Montagnaro, Piero...

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