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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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Main Issues
Cycle #
2 4 6 8 10 12 14
Cap
ture
Cap
acity
DecayofCO2 CaptureCapacityofthesorbent
SinteringPresenceofSO2
CaO +SO2 +½O2→CaSO4
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Main Issues
Cycle #
2 4 6 8 10 12 14
Cap
ture
Cap
acity
DecayofCO2 CaptureCapacityofthesorbent
Sintering
PresenceofSO2
CaO +SO2 +½O2→CaSO4• Externalsulfatelayer• Changeofmechanicalproperty
• Permanentlossofthesorbent
StanmoreandGilot,2005;Blameyetal.,2010;Montagnaroetal.,2010
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Main Issues
circulationofthesolidphasebetweenthereactors
intimatecontactbetweenthesolidandgasphases
CO2 recycledfromtheoutletgas,oraCO2/H2Omixture
comingfromthecombustionprocess
Two Interconnected Fluidized Beds
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Main Issues
Two Interconnected Fluidized Beds
Attrition/FragmentationPhenomena
PrimaryFragmentation
SecondaryFragmentation
AttritionbyAbrasion
Few dataonattrition ofsorbent duringcarbonation/calcination cycles areavailable inthe
literature (Blamey etal.,2010)
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
0.25MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny dolomite
Results:CO2 CaptureCapacity‐ CC
0.02‐0.07gCO2/gSorbent 0.1‐0.2gCO2/gCaCO3Undermilder conditionsBlamey et al.,2010
0.12gCO2/gSorbent
Sintering resistance
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
0.25MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny dolomite
Results:CO2 CaptureCapacity‐ CC
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Results:CO2 CaptureCapacity‐ CC
Intermediate Conditions
Cycle, #
1 2 3 4 50.00
0.05
0.10
0.15
0.20
0.25MassicciSchwabian AlbEnbwXirorema SandTarnow OpolskiCzatkowiceRedziny dolomite
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
Intermediate Conditions
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)
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
Intermediate Conditions
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)
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
Intermediate Conditions
Results:Average Elutriation Loss
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5CalcinationCarbonation
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
Results:Average Elutriation Loss
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
thedolomiteabrasion is muchhigher than limestone
thepresence ofSO2 slightlydecreases theaverage
elutriation loss
‘Limestones’referstotheaveragevaluesofthesixlimestones
SO2=1500ppm
SO2=750/75ppm
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
5CalcinationCarbonation
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
Results:Average Elutriation Loss
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
0.19%
0.23%
0.10%
0.39%
0.23%
0.33%
‘Limestones’referstotheaveragevaluesofthesixlimestones
Conclusions
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
CO2 capture Attrition
Oxi‐firingconditions: strongnegativeeffect positiveeffect
Effect ofSO2 negativeeffect slighteffect
LimestonevsDolomite dolomite limestone
theaveragelimestonelossratebyelutriationisabout0.5%/h
Conclusions
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
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
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Title
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Title
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom
Title
5th High Temperature Solid Looping Network Meeting2-3 September 2013, Cambridge, United Kingdom