Download - Antonio Coppola, Fabio Montagnaro, Piero Salatino ...Antonio Coppola, Fabio Montagnaro, Piero Salatino, Fabrizio Scala Istitutodi Ricerche ... 2 → CaSO 4 5th High Temperature Solid

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


Title
