Post on 06-Feb-2018
Carlos AbanadesSpanish National Research Council
National Coal Institute (Oviedo-Spain)
Calcium Sorbent Cycling for Simultaneous CO2 Capture and Clinker Production
Fundamentals of carbonate looping cycles. The synergy between power and clinker production. Precalcination of CaCO3 with “hot” CaO in a cement plant.
The main CO2 capture systems
Raw material Gas, Ammonia, Steel, Cement
Reformer+ CO2 Sep
Air Separation
CO2Separation
CO2Compression& Dehydration
Power & Heat
Power & Heat
Power & Heat
Process and CO2 Sep.
N2
N2 O2
O2
H2
N2O2
CO2
CO2
CO2
CO2
Air
Post combustion
Pre combustion
Oxyfuel
Industrial Processes
Air
Air
Fuel
Gasification
Gas, Oil
Air/O2Steam
SRCCS, IPCC 2005
Pow
erG
ener
atio
n
Fuel
Fuel
Fuel
STORAGE
Intrinsic benefit of CCS applied to the cement industry
Avoided cost:
COST/unitofProductcapture -COST/unitofProductreference
t CO2 /UnitofProductreference - t CO2 /UnitofProductcapture
$/t CO2 avoided =
It is usually “cheaper” to avoid CO2 in processes with high specific emmisions (like cement manufacture) than in processes of low specific
emmissions
Heat
CalcinerT>870 C
CO2Flue gas“without” CO2
CarbonatorT=600-700C
Flue gas
CaO
CaCO3
The equilibrium of CO2 on CaO
0,001
0,010
0,100
1,000
10,000
100,000
600 700 800 900 1000 1100
T (C)
P co
2, e
q, a
tm
Carbonati
on
Calcination
950 Cº650 ºC
Air CO2
Gas exit
Termopar
Oven control x 2
Flow mass control
CYCLES
Air input
Reactivity drops at increasing number of carbonation calcination cycles
0
0.2
0.4
0.6
0.8
1
0 2 4time (min)
XCaO
cycle 1cycle 10cycle 50cycle 100
Reactivity is strong function of cycle number, temperature, CO2 partial pressure, particle size, impurities, sulphur content, texture of CaO etc.
Sorbent deactivation curves for high number of cycles
Residualactivity
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400 500
cycle number
XCa
O
0
0.2
0.4
0.6
0.8
1
0 20 40
Decay in activity is only a function of cycle number and
SO2 content
(at T<950ºC)
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400 500
cycle number
XCa
O
0
0.2
0.4
0.6
0.8
1
0 20 40
We can work with high make up flows to ensure a large presence these type of particles
Calciner
CO2
Carbonator
Flue gas
Flue gasw/o CO2
CaOCaCO3
CaCO3CaO
Suitable raw feed to a clinker oven
Aplication to existing power plantsPostcombustion looping
Power Plant
Calciner oxyfuelT>900ºC
CO2
Flue gas
Flue gas no CO2
Air
Oxygen
coal
CarbonatorT>600ºC
Coal Air
New oxyfuel CFB power plant
CO2 for transport and geolog. storage
HEAT
Cost structure of the full capture system
New or existing complete power plant
New oxyfired CFBC complete power plant
(+ ASU +CO2 compressor)
~ 0.06 €/kWhe~ 30 €/t CO2
~ 0.04 €/kWhe
Coal A Coal B
CO2 A
CO2 (A+B)Carbonator
Cost of electricity can be around 0.05 €/kWheAvoidance cost of CO2 even below 15 €/tCO2 ( extra CO2 captured as CaCO3 )
Power Plant
Clinker oven
1
Synergies with a cement plant
0.46
0.1
0
Without carbonate looping With carbonate looping
ηpow = 0.46/(1+0.1)=0.42
Power Plant
Clinker oven
10.38
0.030
CaO
ηpow = 0.377/(1+0.03)= 0.37
5 net points of ef. penalty including compression to 100 bar
CaCO3
CaCO3
Clinker Clinker
The capture step generates additional powerEfficiencies penalties intrinsically lowCheap and widely available CO2 sorbentSeveral options are suitable for retrofittingIt can be integrated with O2 combustionIt can/should be integrated with a cement production plantIt can be applied to any fuel
Summary of Potential Benefits
Potential for low capture costs AND very low efficiency penalties
30 kW interconnected fluidized bed carbonate looping system.
(operating from 2007 at INCAR-CSIC)
Acknowledgements(funding projects)
European Commission C3-Capture (2006-2008), ISCC (2004-2006) del VI PM, CCCC (2003-2005) AdvHX (1999-2002) de CECA.CENIT-CO2 (ENDESA-coordinator); module 3 (contract-U Fenosa/CSIC)Contract Hunosa/CSIC for the pre-design of a 1Mwt advanced test facility forCaO looping cycles.
Carlos AbanadesSpanish Research Council
National Coal Institute (Oviedo)
Calcium Sorbent Cycling for Simultaneous CO2 Capture and Clinker Production
Fundamentals of carbonate looping cycles and the synergy between power and clinker production. Precalcination of CaCO3 with “hot” CaO in a cement plant.
Calcination of CaCO3 with high T CaO
Flue gas
CALCINERCALCINERCOMBUSTORCOMBUSTOR
Concentrated CO2
CaCO3
CaOHEATHEAT
Coal Air
CaO
Abanades, 2006 (patent appl.)Rodrírguez et al (EST, 2008)
Clinker oven
950 kg
clinker
66% CaO
1117 kg CaCO3
325 kg marl, clay, shale
Fuel72 kg
Air
(491 from limestone + 172 from fuel)663 kg CO2
1000 kgcement
50 kgadditivies
Precalciner CementGrindingKiln
Fuel48 kg
Air
114 kg CO2
(a) Specific energy: 3 GJ/t cement
950 kg
clinker
66% CaO
1117 kg CaCO3
325 kg marl, clay, shale
Fuel72 kg
Air
(491 from limestone + 172 from fuel)663 kg CO2
1000 kgcement
50 kgadditivies
Precalciner CementGrindingKiln
Fuel48 kg
Air
114 kg CO2
(a) Specific energy: 3 GJ/t cement
950 kg
clinker
1117 kgCaCO3
Fuel95 kg
Air
491 kg CO2
PrecalcinerT=950 ºC
CementGrinding
1000 kg
cement
50 kgadditivies
CombustorT=1050 ºC
228 kg CO2
Kiln
325 kgmarl, clay, shale
625 kg
CaO
CaO
CaOFuel45 kg
Air
107 kg CO2
(b) Specific energy: 3.5 GJ/t cement
950 kg
clinker
1117 kgCaCO3
Fuel95 kg
Air
491 kg CO2
PrecalcinerT=950 ºC
CementGrinding
1000 kg
cement
50 kgadditivies
CombustorT=1050 ºC
228 kg CO2
Kiln
325 kgmarl, clay, shale
625 kg
CaO
CaO
CaOFuel45 kg
Air
107 kg CO2
(b) Specific energy: 3.5 GJ/t cement
M&H balances. Existing vs proposed cement plant
ConcentratedCO2
Prec
alci
ner
T>90
0ºC
Fluegases
Fuel
CaO
CaCO3
Air
Com
bust
or T>
1000
ºC
HighTemperatureCaO stream
CaO, CaSO4Ashes
CompressionTransport
andstorage
ConcentratedCO2
Prec
alci
ner
T>90
0ºC
Fluegases
Fuel
CaO
CaCO3
Air
Com
bust
or T>
1000
ºC
HighTemperatureCaO stream
CaO, CaSO4Ashes
CompressionTransport
andstorage
ΔTcomb-calc
0 50 100 150 200
S/G
5
10
15
20
25
30
Hco
mb
2.25
2.30
2.35
2.40
2.45
2.50
2.55
2.60
2.65
Previous publications
The maximum capture efficiency of CO2 using a carbonation/calcination cycle of CaO/CaCO3. J C Abanades. Chem. Eng. J., 90, 303-306 (2002)Novel combustion cycles incorporating capture of CO2 with CaO; J C Abanades, John E. Oakey; Diego Alvarez; Jouni Hämäläinen, 6th Greenhouse Gas Control Technologies, Kyoto-Japan, October 2002Conversion limits in the reaction of CO2 with lime; J C Abanades, D. Alvarez. Energy and Fuels, Vol 17, 2, 2003, 308-315Progress of Sulfation in Highly Sulfated Particles of Lime; J C. Abanades, E. J. Anthony, F.García-Labiano, L. Jia, Ind. Eng. Chem. Res. 2003, 42, 1840-1844In-situ capture of CO2 in a fluidized bed combustor. J.C. Abanades, E.J. Anthony, D Alvarez, D. Lu. 17th Int. Conf. on Fluidized Bed Combustion, FL-USA, ASME. May 2003. paper10A simulation study for fluidized bed combustion of petroleum coke with CO2 capture. J. Wang, E.J. Anthony, J.C. Abanades 17th Int. Conf. on Fluidized Bed Combustion, FL-USA, ASME. May 2003, paper 169.Novel CO2 control method by means of CO2 chemical looping. C. Salvador, D. Lu, E. J. Anthony and J. C. Abanades. 7th International Conference on Energy for a Clean Environment. 7-10 July Lisbon 2003.Clean and Efficient Use of Petroleum Coke for Combustion and Power Generation. J. Wang, E. J. Anthony, J.C. Abanades. Fuel 83 (2004) 1341–1348Enhancement of CaO for CO2 capture in FBC environment. C. Salvador, D. Lu, E.J. Anthony, J.C. Abanades. Chem. Eng. J. 2003, 96 (1-3) , 187-195.Capture of CO2 from Combustion Gases in a Fluidized Bed of CaO. J.C. Abanades , E. J. Anthony, D. Alvarez, D. Y. Lu, C.Salvador. AIChE J 2004 , Vol 50, No. 7, 1614-1622Investigation of the solid flow between two fluidised beds connected by an orifice. G. Grasa, J. C. Abanades, J. Oakey. Chem. Engng. Sci. 59 (2004) 5869 – 5872Sorbent cost and performance in CO2 capture systems. Juan C. Abanades, Edward S. Rubin, Edward J. Anthony. Ind. Eng. Chem. Res. 2004, (43) 3462-3466 Fluidized bed combustion systems integrating CO2 capture with CaO. J.C. Abanades, E. J. Anthony, J. Wang, J. E. Oakey. Env. Sci. & Tech. 39, 2861-2866 ( 2005)Pore size and shape effect on the recarbonation performance of calcium oxide submitted to repeated calcination/recarbonation cycles. D. Alvarez, JC Abanades, Energy and Fuels 19, 270-278 (2005)Determination of the critical product layer thickness in the reaction of CaO with CO2. D. Alvarez, JC Abanades, Ind. Eng. Chem. Res 2005, 44, 5608Novel capture processes LI. Eide, M. Anheden, A. Lyngfelt, J. C. Abanades, M. Younes, D. Clodic, A. Bill, PHM. Feron Oil & Gas Science and Technology 60(3), 497-508 (2005)Process Optimization in Postcombustion CO2-Capture by means of Repowering and Reversible Carbonation/ Calcination Cycle; Luis M. Romeo, Juan C. Abanades, Juan C. Ballesteros, Antonio Valero, Jesús M. Escosa, Antonio Giménez, Cristóbal Cortés, Jara Paño; 8th International Congress on Greenhouse Gas Control Technologies-GHGT-8, Norway 2006The kinetics of carbonation of CaO particles cycling in a CO2 capture loop; G. Grasa, J.C. Abanades8th International Congress on Greenhouse Gas Control Technologies- GHGT-8, Norway 2006CO2 capture capacity of CaO in long series of carbonation/calcination cycles; G. Grasa, J.C. Abanades, Ind. Eng. Chem. Res. 45, 8846Economics of CO2 Capture Using the Calcium Cycle with a Pressurized Fluidized Bed Combustor ; A. MacKenzie, D. L. Granatstein, E. J. Anthony, and J. C. AbanadesEnergy & Fuels 21, 2007The cost structure of a postcombustion CO2 capture system using CaO; Abanades, J.C.; Grasa, G.; Alonso, M.; Rodríguez, M.; Anthony, E.J. Enviromental Science and Technology 41(15), 5523, 2007Comparison of CaO-Based Synthetic CO2 Sorbents under Realistic Calcination Conditions ; Grasa, G.S.; González, B.; Alonso, M.; Abanades, J.C. Energy and Fuels, 2007, doi: 10.1021/ef0701687Heat requirements of a CaCO3 calciner when integrated in a CO2 capture system.; Rodríguez, N.; Alonso, M.; Grasa, G.; Abanades, J.C. ; Chemical Engineering Journal In press doi:10.1016/j.cej.2007.06.005)Reactivity of highly cycled particles of CaO in a carbonation/calcination loop ; Grasa, G.S.; Abanades, J.C.; Alonso, M.; González, B. Chemical Engineering Journal, in press: doi:10.1016/j.cej.2007.05.017Páginas, Oxyfuel carbonation/calcination cycle for low cost CO2 capture in existing power plants; Luis M. Romeo, J. Carlos Abanades, Jesús M. Escosa, Jara Paño; Energy Conversión and Management, 2008 (in press)Sulphation of CaO particles in a carbonation/calcination loop to Capture CO2; Grasa G.; Alonso, M.; Abanades, J.C. Ind. Eng. Chem. Res., 2008 (in press)
Carbonate looping cycles are a one of the most promising concepts to capture CO2 from a power plantThey can operate using cheap, natural limestones, but a large make up flow (and purge of CaO) is required Early oportunities for application of carbonate looping at large scale will require oxycombustion calcination and synergy with a cement plant. There is potential for even lower cost and high efficiency CaO looping concepts (no Oxycombustion required). In particular for CaCO3 precalcination.
Conclusions
There is an increasing interest worldwide for carbonate looping R&D