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Prof. J. Carlos Abanades Spanish Research Council, CSIC-INCAR
Experiences from la Pereda pilot plant
1st Public SCARLET Workshop, Darmstadt University, 20th April 2016
Outline
Description of the 1.7 MWth pilot of la Pereda
Example of results and main trends
Potential improvements on postcombustion CaL
0.03 MWth pilot at INCAR-CSIC
Twin CFB reactor concept validation in
lab scale. Basic reactor and process modeling
From 2008 “La Pereda 1.7 MWth” pilot
From 2012
Reactions kinetics, deactivation studies, reactivation methods
Multicycle testing TG at CSIC
From 2000 Abanades and Alvarez, 2003.
Conversion limits in the reaction of CO2 with lime. Energy and Fuels, 17-
2, 308 -315
Rodriguez et al. 2010. Experimental investigation of a CFB reactor to capture CO2 with CaO. AIChe Journal, 57, pp. 1356 - 1366
Arias et al. 2013. Demonstration of steady state CO2 capture in a 1.7 MWth calcium looping pilot. Int. J. of Greenhouse Gas Control 18, 237–245
CSIC & the development of CaL technology
The 1.7 MWth CaL pilot at la Pereda
La Pereda Power plant: CFBC technology, 50 MWe La Pereda Power plant: CFBC technology, 50 MWe 2009-2012
2013-2015
2015-2017
LA PEREDA CO2 CAPTURE PILOT PLANT: DESCRIPTION
Calciner operating under air or oxy-combustion conditons
Double loop seal to control solid circulation between
reactors
Removable cooling bayonet tubes to change heat extraction in reactors
O2 and CO2 tanks and gas mixer, to change oxy-
combustion ratio
Calciner gas heater and indepent steam inyection
Continuous coal and limestone feeding system
Reactor Characteristics: •Height: 15 m •Made of refractory and Carbon Steel •High efficiency cyclones •Fully instrumentallized
Range of conditions during the CO2 capture test:
RESULTS
Carbonator temperature (ºC) 600-750 Carbonator superficial gas velocity (m/s) 2.0-6.0 Inlet CO2 volume fraction to the carbonator 0.12-0.14 Inlet SO2 concentration to the carbonator (mg/m3) 100-250 Inventory of solids in the carbonator (kg m-2) 100-1000 Maximum CO2 carrying capacity of the solids 0.10-0.50 Calciner temperature (ºC) 820-950 ºC Inlet O2 volume fraction to the calciner 0.21-0.35 Inlet CO2 volume fraction to the calciner 0-0.75 CO2 capture efficiency 0.4-0.95 SO2 capture efficiency 0.95-1.00
Operating conditions and results as expected in large scale systems
Outline
Description of the 1.7 MWth pilot of la Pereda
Example of results and observed trends
Potential improvements on postcombustion CaL
Publications of results from la Pereda pilot
• Demonstration of steady state CO2 capture in a 1.7 MWth calcium looping pilot; B Arias, ME Diego, JC Abanades, M Lorenzo, L Diaz, A. Sanchez, D Martínez, Int. Journal of Greenhouse Gas Control 18, 237-245, 2013.
• Emerging CO2 capture systems. J.C. Abanades, B. Arias, A. Lyngfelt, T. Mattisson, D.E. Wiley, H. Li, M.T. Ho, E. Mangano, S. Brandani; Int. Journal of Greenhouse Gas Control, 2015, vol 40, 126-166
• Experimental testing of a sorbent reactivation process in La Pereda 1.7 MWth calcium looping pilot plant ME Diego, B Arias, A Mendez, J.C. Abanades, M Lorenzo, L Diaz, A. Sanchez; Int. Journal of Greenhouse Gas Control, 2016, in press
• 2 book chapters • > 5 international conference proceedings
Results from the 1.7 MWth CaL pilot plant of la Pereda
B Arias, et al., Int. Journal of Greenhouse Gas Control 18, 237-245, 2013.
Example of steady state of CO2 capture
0
0.2
0.4
0.6
0.8
1
12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00
CO2 c
aptu
re e
ffici
ency
0
2
4
6
8
10
12
14
CO2 (
%vo
l)ECO2 eqECO2CO2 outCO2 in
- Inventory of solids in carbonator = 300-400 kg/m2 - Average carbonator temperature= 660 ºC - Xave = 0.3-0.1
>1500 h Operating in CO2 capture mode
Arias et al. 2013. Demonstration of steady state CO2 capture in a 1.7 MWth calcium looping pilot. Int. J. of Greenhouse Gas Control 18, 237–245
RESULTS
Typical example of steady state tests
CARBONATOR - Average carbonator temperature= 660 ºC - Inlet gas velocity= 3.5 m/s
OXYFIRED CALCINER - Average carbonator temperature= 915 ºC - Average gas velocity= 4.7 m/s
0.0
0.2
0.4
0.6
0.8
1.0
19:00 19:30 20:00 20:30 21:00 21:30 22:00 22:30 23:00
CO
2 cap
ture
eff
icie
ncy
0
2
4
6
8
10
12
14
Carb
onat
or C
O2
(%)
CO2 equilibriumCO2 experimentalCO2 inCO2 out
0
20
40
60
80
100
19:00 19:30 20:00 20:30 21:00 21:30 22:00 22:30 23:00
Calc
iner
CO
2 (%
)
0
10
20
30
40
50
60
Calc
iner
SO
2 (pp
m)
CO2 out
SO2 out
ECO2 ECO2
Effect of average sorbent activity on CO2 capture efficiency (Oxyfuel combustion-calcination mode)
Results from the 1.7 MWth CaL pilot plant of la Pereda
ucarb = 4.0-4.3 m/s Tcarb = 660-690ºC Xave = 0.21 Xave = 0.11
Closure of carbon mass balances CO2 mass balance in the system
CO2 reacting with CaO in the bed
CO2 removed from the gas phase
CaCO3 formed in the circulating stream of CaO = = CO2 produced by
calcination =
0
2
4
6
8
10
12
11:30 12:30 13:30 14:30 15:30 16:30
CO2 f
low
(km
ol/h
)
CO2 produced by calcination
CO2 captured in the carbonator
Basic reactor models: -Perfect mixing of solids -Plug flow of gas Reaction rate
CO2 mass balance closure
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
CaCO3 formed in the circulation of solids (mol/m2s)
CO2 r
emov
ed fr
om th
e ga
s pha
se (m
ol/m
2 s)
CO2 reacting with CaO in the bed
CO2 removed from the gas phase
CaCO3 formed in the circulating stream of CaO = =
( )e2COavesXkdtdX
ν−ν=
aveaCO
CaOactive Xf
FN
2
=τ
Arias et al. 2013. IJGGC 18, 237–245
Modelling of a fluidized bed carbonator reactor to capture CO2 from a combustion flue gas M Alonso, N Rodríguez, G Grasa, JC Abanades Chemical Engineering Science 2009, 64 (5), 883-891
Experimental investigation of a circulating fluidized‐bed reactor to capture CO2 with CaO N Rodríguez, M Alonso, JC Abanades AIChE Journal 2011, 57 (5), 1356-1366
Experimental validation of the calcium looping CO2 capture process with two circulating fluidized bed carbonator reactors. A. Charitos, N Rodríguez, C Hawthorne, M Alonso, et al Ind. & Engng.Chem. Res. 2011 50 (16), 9685-9695
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0τactive normalized
E CO
2 nor
mal
ized
Experimental
Calculated
CO2 mass balance closure
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
CaCO3 formed in the circulation of solids (mol/m2s)
CO2 r
emov
ed fr
om th
e ga
s pha
se (m
ol/m
2 s)
aveaCO
CaOactive Xf
FN
2
=τ
CO2 reacting with CaO in the bed
CO2 removed from the gas phase
CaCO3 formed in the circulating stream of CaO = =
Arias et al. 2013. Demonstration of steady state CO2 capture in a 1.7 MWth calcium looping pilot. Int. J. of Greenhouse Gas Control 18, 237–245
0.80
0.85
0.90
0.95
1.00
3:00 5:00 7:00 9:00 11:00 13:00 15:00
E SO
2
0
0.03
0.06
0.09
0.12
0.15
X CaS
O4
ESO2 carb
ESO2 calc
ExperimentalCalculated
RESULTS FROM THE 1.7 MWth CALCIUM LOOPING PILOT PLANT OF LA PEREDA
0,0
0,2
0,4
0,6
0,8
1,0
0,0 0,2 0,4 0,6 0,8 1,0
CO2 capture efficiency
SO2 c
aptu
re e
ffici
ency
SO2 mass balance in the system SO2 reacting with
CaO in the bed SO2 removed from
the gas phase CaSO4 formed in the
circulating stream of CaO = = CaSO4 in the purge of solids =
Accumulation of CaSO4 in the
inventory of solids
Investigation of SO2 capture in a circulating fluidized carbonator of a Ca Looping cycle B. Arias et al. Industrial & Engineering Chemistry Research, 2013, 52, 2700−2706
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 5 10 15 20 25 30 35
N th
X ave
, XN, X
CaSO
4
XaveXN (Grasa et al 2006)XCaSO4 experimentalXCaSO4 calculatedCaO utilization
0
0.2
0.4
0.6
0.8
1
11:10 11:20 11:30 11:40 11:50 12:00
E CO
2
0
200
400
600
800
1000
1200
Inve
ntor
y of
solid
s (kg
/m2 )
ECO2 eq
ECO2
Carbonator inventory
Evolution of sorbent utilization with “lifetime” of particles in the system
dtXN
EFN
t
aveCa
tcarbCOth ∫= 0
)(2Number of times that the inventory of CaO is carbonated up to the maximum CO2 carrying capacity
RESULTS FROM THE 1.7 MWth CALCIUM LOOPING PILOT PLANT OF LA PEREDA
Outline
Why post-combustion CO2 capture by CaL ?
Fundamentals and current status of CaL
Potential improvements on postcombustion CaL . Improving sorbent activity . Reducing heat demand in the calciner . Other reactor designs and adaptation to other industries (cement)
Pilot experiments with recarbonation
http://recal-project.eu/
Carb
onat
or
Calc
iner
Loop seal-Recarbonator
‘Novel Calcium looping CO2 capture process incorporating sorbent reactivation by Re-carbonation’ EU RFCS project: 2012-2015
0.15
0.00
0.04
0.08
0.12
0.16
0.20
10:00 12:00 14:00 16:00 18:00 20:00
X
Time
Xr - Xsulf
Xave - Xsulf
Xave,R (exp.)
0.00
0.04
0.08
0.12
0.16
0.20
18:00 20:00 22:00 0:00 2:00 4:00 6:00 8:00
X
Time
Xr - Xsulf
Xave - Xsulf
Xave,R (exp.)0.08
The sorbent activity doubles due to recarbonation
Initial tests with recarbonation
Arias et al 2012. Energy & Env.Sci., 5, pp. 7353-7359 Grasa et al. 2014. I&EC Research 28, pp. 4033 - 4042 Diego et al. 2014. Energy Procedia 2015, GHGT12 Diego et al. 2016 I. Journal Greenhouse Gas Control, Volume 50, July 2016, Pages 14-22
CO2
<20% of heat demand in the calciner by increasing the oxygen
concentration up to 80%v
New process configuration with: -Less oxygen requirement (less OPEX) -Reduced size of calciner and ASU (less CAPEX)
CaO2 : Calcium looping CO2 capture technology with extreme oxy-coal combustion conditions in the calciner European Union RFCS project: 2014-2017 2015-2017
Calcination of CaCO3 with “superheated” CaO
Diego et al. Analysis of a double calcium loop process configuration for CO2 capture in cement plants Journal of Cleaner Production Volume 117, 20 March 2016, Pages 110–121
2002
Concluding remarks
Postcombustion Calcium Looping (CaL) has been succesfuly tested in several continuous large scale pilots for 1000s of hours.
Standard configurations of CaL, using highly mature process components, could be retrofitted to existing power plants, achieving capture efficiencies around 90%, energy penalties 6-8 net points and cost about 20-30% lower than oxyfired CFBCs.
There is scope for substantial reductions in penalty and costs: i.e. by reducing heat demand in the calciner through new reactor and process designs and by integration with other industries (i.e. cement ).
IF there was a market for CCS, Calcium looping technologies could be scaled up quickly by exploiting similarities with CFBCs
Secondary air
ROTARY KILN CLINKER COOLER
CLINKER GRINDING
PRE-HEATINGSTAGES
Limestone
CO2-lean flue gas
Coal
Pet cokePrimary air
CaO
Kiln flue gas
Concentrated CO2
ClayShale
Air
Excess air
Hot clinker
Cold clinker
Additives
Cement
CARB
ON
ATO
R
CALC
INER
ASU
CaCO3 CaO
Air O2
CaCO3
Other process variants: CaL for cement plants
2015-2018