PROGRESS ON THE CALCIUM LOOPING POSTCOMBUSTION PROCESS

PROGRESS ON THE CALCIUM LOOPING POSTCOMBUSTION PROCESS Carlos Abanades abanades@incar.csic.es CO 2 Capture Group Spanish Research Council (INCAR CSIC)

Outline Why post combustion CO 2 capture by CaL? Current status of postcomb CaL Potential improvements on postcombustion CaL

CaL post combustion process scheme Shimizu et al, Trans IChemE, Vol 77, Part A, January 1999

CaL post combustion process Figure adapted from Dieter et al (Fuel, 127, 23-37, 2014) Conventional power plant New Calcium oxy fired looping CFBC system power plant Benefits of Ca looping Low energy penalty (6 8 net points) and low cost per ton CO 2 captured Low cost sorbent precursor Purge of CaO: synergies with cement industry and others (i.e. desulfurization ) Pre treatment of flue gas no needed (SO 2 co capture) Suitable for retrofitting to existing power plants

Outline Why CaL for post combustion CO 2 capture? Current status of postcomb CaL Potential improvements on postcombustion CaL

Current status of postcomb CaL Number of papers in Scopus under Calcium looping or Carbonate looping

Current status of postcomb CaL http://www.sciencedirect.com/science/journal/17505836 OPEN ACCESS DURING SEPTEMBER 2015

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, 2015, vol 40, 126 166 doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant www.itri.org.tw From: Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu No results published yet Challenging calciner design and bubbling Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). La Pereda (Spain) Darmstad (Germany) IFK (Germany) La Robla (Spain) ITRI (Taiwan) Thermal input 1.7 MWth referred to 1 MWth referred to calciner 50 230 kwth referred to 300 kwth referred to the biomass fed to 1.9 MWth (1 tco2/h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m0.9 Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m On:Off loop seal Kiln rotation speed Flue gas generated in Integrated with the cement plant Air fired with biomass Oxy fired with diesel 1.0 0.8 80 Control of solid 60 flow Flue gas source 40 Calciner Integrated with power plant Flue gas from 0.5 coal burner Synthetic flue gas Oxy fired with coal Oxy fired coal/propane Oxy fired http://recal project.eu/ ; http://cao2.eu or website Experimental 0 21:00 21:15 0.7 Cone valves 0.6 Screw conveyors operation 20 Project name Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Cone valves 21:30 Ecarb/Eeq CO2 capture efficiency (%) 100 Diameter 0.4 with 21:45 22:00 with coal 0.3 and flue gas recyclelarobla http://www.project 0.2 scarlet.eu/ Equilibrium m http://cal mod.eu projects.de/ 0.1 0.0 0.00 0.05 MenosCO2 INCAR post-combustion combustion-carbonation 0.10 τactive (h) Alonso et al., Int. J. Greenhouse Gas Control 29(2014) 142 152 Diego et al. 22nd FBC Conf Turku, Finland, June 2015 0.15 HECLOT 0.20

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). Thermal input Configuration Height Diameter Control of solid flow Flue gas source Calciner operation Project name or website La Pereda (Spain) 1.7 MW th referred to Calciner: 15 m Carbonator: 15 m Calciner: 0.75 m Carbonator: 0.65 m Darmstad IFK (Germany) La Robla (Spain) ITRI (Taiwan) (Germany) DIETER, H., et al. 1 MW th referred todevelopment 50 230 kw th referred of the calcium 300 kw th referred to 1.9 MW th (1 t CO2 /h) calciner to the biomass fed to looping CO2 capture technology from lab to pilot scale Calciner: at CFB IFK, University Calciner: of CFB Calciner: rotary kiln Carbonator: FFB* and Carbonator: FB Stuttgart. TFB* Fuel, 127, 23-37 Calciner: 11.4 m Calciner: 10 m Calciner: 12 m Calciner: 5m (length) Carbonator: 8.6 m Carbonator: 10 m Carbonator: 12 m Carbonator: 2.5m (FFB*), 6 m (TFB*) Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m DIETER, H., SCHEFFKNECHT, G. Cone valves Screw conveyors This ConeHTSLC valves meeting, On:Off 2015 loop seal Kiln rotation speed today at 11:50 Integrated with power Flue gas from coal Synthetic flue gas Flue gas generated in Integrated with the plant burner cement plant Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Air fired with biomass MenosCO2 Oxy fired with diesel HECLOT From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT STRÖHLE, J., JUNK, M., KREMER, J., GALLOY, A. & EPPLE, B. 2014. Carbonate looping experiments in a 1 MWth pilot plant and model validation. Fuel, 127, 13 22. From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kwth). Thermal input La Pereda (Spain) 1.7 MW th referred to Darmstad (Germany) 1 MW th referred to calciner IFK (Germany) La Robla (Spain) ITRI (Taiwan) 50 230 kw th referred to 300 kw th referred to the biomass fed to 1.9 MW th (1 t CO2 /h) Configuration Carbonator: FFB* and TFB* Calciner: rotary kiln Carbonator: FB Height Calciner: 15 m Carbonator: 15 m Calciner: 11.4 m Carbonator: 8.6 m Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*) Calciner: 12 m Carbonator: 12 m Calciner: 5m (length) Carbonator: 2.5m Diameter Calciner: 0.75 m Carbonator: 0.65 m Carbonator: 0.59 m Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+) Carbonator: 0.4 m Calciner: 0.9 m Carbonator: 3.3 m Control of solid flow Flue gas source Calciner operation Project name or website Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed Integrated with power plant Flue gas from coal burner Oxy fired with coal Oxy fired with coal/propane http://recal project.eu/ ; http://cao2.eu Synthetic flue gas Oxy fired with coal and flue gas recycle http://www.projectscarlet.eu/ http://cal mod.euprojects.de/ Flue gas generated in Air fired with biomass MenosCO2 Integrated with the cement plant Oxy fired with diesel HECLOT From: Abanades et al, Emerging CO 2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

Development of CaL technology in la Pereda Process concept Reactions kinetics, sorbent deactivation, reactivation methods Twin CFB concept validation in lab pilot plants Reactor modeling, Twin CFB demon at large pilot scale 1999 process integration 2008 2012 Multicycle testing TG at CSIC 0.03 MW th pilot at INCAR CSIC La Pereda 1.7 MW th pilot Abanades and Alvarez, 2003. Conversion limits in the reaction of CO 2 with lime. Energy and Fuels, 17-2, 308-315 Rodriguez et al. 2010. Experimental investigation of a CFB reactor to capture CO 2 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

Description of the 1.7 MW th pilot La Pereda Power plant: CFBC technology, 50 MWe

Example of steady state of CO 2 capture CO2 capture efficiency 1 0.8 0.6 0.4 0.2 0 ECO2 eq ECO2 CO2 out CO2 in >1200 h Operating in CO 2 capture mode 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 14 12 10 8 6 4 2 0 CO2 (%vol) Inventory of solids in = 300 400 kg/m2 Average temperature= 660 ºC Xave = 0.3 0.1 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

CO 2 mass balance closure CaCO 3 formed in the CO 2 removed from circulating stream of CaO= the gas phase = CO 2 reacting with CaO in the bed CO2 removed from the gas phase (mol/m 2 s) 8 7 6 5 4 3 2 1 ECO2 normalized 1.0 0.8 0.6 0.4 0.2 Basic reactor models: Perfect mixing of solids Plug flow reactor Reaction rate dx k X s ave CO2 e dt active N F CaO CO2 Experimental Calculated f a X ave 0 0 1 2 3 4 5 6 7 8 CaCO 3 formed in the circulation of solids (mol/m 2 s) 0.0 0.0 0.2 0.4 0.6 0.8 1.0 active normalized 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

Outline Why CaL for post combustion CO 2 capture? Current status of postcomb CaL Potential improvements on postcombustion CaL

Outline Why CaL for post combustion CO 2 capture? Current status of postcomb CaL Potential improvements on postcombustion CaL. Improving sorbent activity. Reducing heat demand in the calciner. Alternative reactors and adaptation to other industries (cement)

Sorbent reactivation by recarbonation Recarbonation is based on the observations of Barker in 1973 Reactivation in one cycle Reactivation in each cycle X N 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 Short carbonation in pure CO 2 One carbonation cycle of 24 h Mol fraction of CaCO 3 1 0.8 0.6 0.4 0.2 Carbonation during 24 h in pure CO 2 Short carbonation in pure CO 2 0,0 0 10 20 30 40 Number of cycles 0 0 5 10 15 20 25 30 Cycle number Barker 1973. The reversibility of the reaction CaCO 3 CaO+CO 2. Journal of Applied Chemistry and Biotechnology, 23, pp. 733 742.

Pilot experiments with recarbonation Novel Calcium looping CO 2 capture process incorporating sorbent reactivation by Recarbonation EU RFCS project: 2012 2015 Loop seal Re X Initial tests with recarbonation 0.20 0.16 0.12 0.08 X ave,r (exp.) 0.15 X ave X sulf 0.04 X r X sulf Calciner Carbonator 0.00 10:00 12:00 14:00 16:00 18:00 20:00 Time 0.20 0.16 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 X 0.12 0.08 0.04 X ave,r (exp.) X ave X sulf 0.08 http://recal project.eu/ X r X sulf 0.00 18:00 20:00 22:00 0:00 2:00 4:00 6:00 8:00 Time The sorbent activity doubles due to recarbonation

CaO 2 : Calcium looping CO 2 capture technology with extreme oxy coal combustion conditions in the calciner European Union RFCS project: 2014 2017 <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)

Novel CaL systems with low (or zero) O 2 in calciner

Novel CaL systems with low (or zero) O 2 in calciner M. Junk, B. Epple Design of a 300 kwth indirectly heated carbonate looping test facility, 5th High Temperature Solid Looping Network Meeting, Cambridge (UK) 2 3 September 2013

CaL systems with reduced (or zero) O 2 in calciner Diego et al. TCCS 8, Trondheim, June 2015

Chemical Looping Combustion applied to the calcination of CaCO 3 Calcination of CaCO 3 by indirect heating Dense solids (iron-based materials) act as oxygen carriers and heat carriers Air reactor performs as CFB reaching temperatures around 1100 ºC Fuel reactor performs as bubbling fluidized bed to allow complete fuel and solids conversion and subsequent solids segregation (T FR =850-900 ºC) Iron-based carriers are cheap, stable at high temperatures and chemically compatible with cement clinker (segregation in-efficiencies are acceptable) Fernández et al. Journal of Cleaner Production. 2015. In press doi:10.1016/j.jclepro.2015.06.010 Patent application WO 2015015042 A1. Priority date: 04/03/2014

Concluding remarks Postcombustion Calcium Looping (CaL) has been tested in continuous large scale pilots (>100 kw th ) for more than 2000 hours. Standard configurations of CaL, using highly mature process components, can be retrofitted to existing power plants with capture efficiencies around 90%, energy penalties 7 8 netpoints and cost about 20 30% lower than oxyfired CFBC s. Scope for substantial reductions in penalty and costs, mainly by: reducing heat demand in the calciner through new reactor and process designs and integration in other industries (cement?). Sorbent related issues are no longer critical for standard postcombustion CaL but need revisiting for novel post and pre combustion CaL systems.