1 1 Options for calcium looping for CO 2 capture in the cement industry G. Cinti 1, R. Matai 2, S. Becker 2, M. Alonso 3, C. Abanades 3, M. Spinelli 4, E De Lena 4, S. Consonni 4, M. Romano 4, M. Hornberger 5, R. Spörl 5 1 Italcementi, Bergamo, Italy 2 IKN GmbH, Neustadt, Germany 3 Agencia Estatal Consejo Superior de Investigaciones Cientificas (CSIC), Madrid, Spain 4 Politecnico di Milano, Milan, Italy 5 Institute of Combustion and Power Plant Technology (IFK), University of Stuttgart, Stuttgart, Germany 2nd ECRA/Cemcap workshop: Carbon Capture Technologies in the Cement Industry Dusseldorf, 6-7 November 2017
2 WP12 participants Institute of Power Plant and Combustion technology, University of Stuttgart Spanish research council, INCAR-CSIC Politecnico di Milano, Department of Energy IKN, Italcementi
3 Calcium Looping process fundamentals CO 2 -lean flue gas CO 2 -rich gas to sequestration CARBONATION CaCO 3 CALCINATION Heat CaO+CO 2 CaCO 3 CaCO 3 CaO+CO 2 Heat ~ 650ºC CaO (F R ) ~ 900ºC Flue gas (CO 2 ) (F CO2 ) CaCO 3 make-up (F 0 ) CaO purge
4 Calcium Looping for CO 2 capture: history Originally proposed by Shimizu et al., 1999. A twin fluid-bed reactor for removal of CO 2. Chem. Eng. Res. Des., 77. Continuously developed since 1998, mainly for application in power plants Several fluidized bed pilot facilities - demonstrated up to 1.7 MW 200 kw pilot at IFK, U. Stuttgart 1 MW pilot at TU Darmstadt 1.7 MW pilot at La Pereda (ES)
5 Calcium looping for cement plants 1. Cement plant-power plant coupling: CaO-rich spent sorbent from a CaL power plant as feed for the cement plant, as substitute of CaCO 3 2. Post-combustion tail end configuration: CaL process is integrated in the cement plant with a conventional post-combustion capture configuration 3. Highly integrated CaL configuration: the CaL process is integrated within the cement production process by sharing the same oxyfuel calciner
6 Cement plant-power plant coupling CO 2 lean flue gas Bolier F CO2 raw meal preheater coal fuel clinker coal F 0 Calcined raw meal
Substitution ratio (% of Ca fed to the cement kiln as CaO from the power plant) 7 Cement plant-power plant coupling Romano M.C. et al., 2013. The calcium looping process for low CO 2 emission cement and power. Energy Procedia, 37, 7091-7099.
Calciner Carbonator 8 Calcium Looping CO 2 capture: Tail-end CaL configuration General features of the process: Carbonator removes CO 2 from cement plant flue gas Easy integration in existing cement Limestone partly calcined in Calcium Looping calciner CaO-rich purge from CaL calciner used as feed for the cement kiln High fuel consumption (double calcination for the mineral CO 2 CaCO 3 CO 2 to CPU O 2 fuel CaO CO 2 depleted flue gas Flue gas Raw meal CEMENT plant captured) Heat from fuel consumption recovered in efficient (~35% efficiency) steam cycle for power generation CFB CaL reactors: d 50 =100-250 μm, vs. particle size for clinker production d 50 =10-20 μm CaL purge milled in the raw mill at low temperature clinker
9 Calcium Looping CO 2 capture: Tail-end CaL configuration Conducted Work: Parameter screening at 30 kw scale at CSIC (TRL5) Demonstration at semi-industrial scale (200 kw th ) at IFK (TRL6) Process simulation and integration Conventional cement kiln components RAW MEAL FAN FILTER FAN LIMESTONE MILL FAN CaL Limestone RAW MEAL SILOS FLUE GAS COOLER LIMESTONE MILL 21 RAW MILL Limestone 1 + correctives COAL SILOS 41 Exhausts from clinker cooler 35 Calciner primary & transport air 36 38 37 Kiln primary & trasport air 39 III Air ROTARY KILN 42 II Air 45 CLINKER COOLER Clinker COOLER FANS 40 Inlet Air 25 CaO-Rich Meal 26 PREHEATING TOWER 29 30 33 18 20 8 ID FAN HT CO2 HT CO2 COOLER 1 COOLER 2 11 14 27 10 12 CARBONATOR CALCINER 28 CO2 FAN 3 15 13 31 22 23 19 9 6 24 7 Coal 32 PURGE COOLER PRECALCINER 2 CaL Purge 34 43 CPU Vent Gas 16 4 ASU 5 Vent LT CO2 COOLER CO2 Compression 17 and Purification Unit CaL CO2 capture island 44 Liquid CO2 Arias et al., 2017. CO 2 Capture by CaL at Relevant Conditions for Cement Plants: Experimental Testing in a 30 kw Pilot Plant. Ind. Eng. Chem. Res., 56, 2634 2640. Hornberger et al., 2017. CaL for CO 2 Capture in Cement Plants Pilot Scale Test. Energy Procedia, 114, 6171 6174. Spinelli et al., 2017. Integration of CaL systems for CO 2 capture in cement plants. Energy Procedia, 114, 6206-6214. De Lena et al. Process integration of tail-end CaL for CO 2 capture in cement plants. Int J Greenh Gas Control. In press.
10 Calcium Looping CO 2 capture: Tail-end CaL configuration Active space time design rule: τ active = N CaO N CO2 f a X ave Amount of active sorbent in the bed τ active > 50 1 s for 90 % CO 2 capture N CaO : molar amount of CaO in Carbonator Ṅ CO 2 : molar flow of CO 2 entering the Carbonator f a : sorbent fraction reacting in fast reaction regime X ave : average sorbent CO 2 carrying capacity
11 Calcium Looping CO 2 capture: Tail-end CaL configuration Demonstration at semi-industrial scale: High CO 2 capture up to 98 % demonstrated Favorable CaL operation conditions reduced recycle train high sorbent activity High CO 2 capture at carbonator inlet may cause problems of entrainment due to reduction of fluidization gas (~ -25 %)
Calciner Carbonator 12 Calcium Looping CO 2 capture: highly integrated configuration CO 2 -rich gas to CPU Fresh raw meal CO 2 -lean flue gas Fresh raw meal General information: CaL calciner coincides with the cement kiln pre-calciner Raw meal preheater CO 2 recycle Calcined raw meal to carbonator Raw meal recycle Raw meal preheater II Calcined raw meal as CO 2 sorbent in the carbonator Sorbent has small particle size (d 50 =10-20 μm) entrained flow reactors Fresh raw meal Raw meal preheater III III Air Marchi M.I., et al., 2012. Procedimento migliorato per la produzione di clinker di cemento e relativo apparato. Patents MI2012 A00382 and MI2012 A00382. Fuel O 2 Calcined raw meal to rotary kiln Recarbonated / fresh sorbent to calciner Rotary kiln Fuel Romano et al., 2014. The calcium looping process for low CO 2 emission cement plants. Energy Procedia, 61, 500-503.
CO 2 capture efficiency 13 Calcium Looping CO 2 capture: highly integrated configuration Conducted Work: TGA sorbent characterization (Re)carbonation experiment in EF conditions EF oxyfuel calcination experiments Simulation of entrained flow Calcium Looping Preliminary process integration study 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Cooled Reactor Adiabatic Reactor 15 kg sorbent /Nm 3 gas 10 kg sorbent /Nm 3 gas 5 kg sorbent /Nm 3 gas 0 20 40 60 80 100 120 140 Reactor length, m
14 Tail end vs. highly integrated configuration: preliminary H&M balance Cement plant integrated Tail-end CaL w/o capture CaL F 0 /F CO2 -- 0.16 4.1 F Ca /F CO2 -- 4.8 4.0 Carbonator CO 2 capture efficiency [%] -- 88.8 80.0 Total fuel consumption [MJ LHV /t clk ] 3223 8672 4740 Rotary kiln burner fuel consumption [MJ LHV /t clk ] 1224 1210 1180 Pre-calciner fuel consumption [MJ LHV /t clk ] 1999 1542 CaL calciner fuel consumption [MJ LHV /t clk ] -- 5920 Net electricity production [kwh el / t clk ] -132 159-164 Direct CO 2 emissions [kg CO2 /t clk ] 863.1 143.2 71.4 Indirect CO 2 emissions [kg CO2 /t clk ] 105.2-123.5 128.7 Equivalent CO 2 emissions [kg CO2 /t clk ] 968.3 19.7 200.1 Equivalent CO 2 avoided [%] -- 98.0 79.3 SPECCA [MJ LHV /kg CO2 ] -- 3.26 2.32 3560 Spinelli M. et al., 2017. Integration of Ca-Looping systems for CO 2 capture in cement plants. Energy Procedia, 114, 6206-6214.
2nd ECRA/Cemcap workshop Dusseldorf, 6-7 November 2017 The CLEANKER project G. Cinti a, M. Fantini b, M. Romano c, F. Canonico d, S. Consonni b,c a Italcementi, Heidelberg Group b LEAP c Politecnico di Milano d Buzzi Unicem
Summary Project objectives The demo plant The consortium Work packages The CLEANKER project 16 16
Primary project objectives The ultimate objective of CLEANKER is advancing the integrated Calcium-looping process for CO 2 capture in cement plants. This fundamental objective will be achieved by pursuing the following primary targets: Demonstrate the integrated CaL process at TRL 7, in a new demo system connected to the operating cement burning line of the Vernasca 900.000 ton/y cement plant, operated by BUZZI in Italy. Demonstrate the technical-economic feasibility of the integrated CaL process in retrofitted large scale cement plants through process modelling and scale-up study. Demonstrate the storage of the CO 2 captured from the CaL demo system, through mineralization of inorganic material in a pilot reactor of 100 litres to be built in Vernasca, next to the CaL demo system. The CLEANKER project 17 17
Vernasca plant location VERNASCA PLANT The CLEANKER project 18 18
Primary project objectives TRL 1 basic principles observed TRL 2 technology concept formulated TRL 3 experimental proof of concept TRL 4 technology validated in lab TRL 5 technology validated in relevant environment (industrially relevant environment in the case of key enabling technologies) TRL 6 technology demonstrated in relevant environment (industrially relevant environment in the case of key enabling technologies) TRL 7 system prototype demonstration in operational environment TRL 8 system complete and qualified TRL 9 actual system proven in operational environment (competitive manufacturing in the case of key enabling technologies; or in space) The CLEANKER project 19 19
Indicative configuration of the CLEANKER pilot Entrained-flow carbonator TO THE PROCESS FILTER Temperature about 400 C Temperature about 650 C MEAL TO PREHEATER GAS FROM PREHEATING TOWER MEAL TO PREHEATER FUEL MEAL 1 t/h Tamb Entrained-flow oxyfuel calciner OXYGEN CO2 CO2 TO THE PROCESS FILTER The CLEANKER project 20 20
Vernasca kiln preheater and rendering of CaL pilot The CLEANKER project 21 21
The consortium 5EU member states + Switzerland The CLEANKER project 22 22
Work packages WP1 - Management WP2 Demonstration system design WP3 Demonstration of CaL process WP4 Comparative characterization of raw meals for CaL WP5 Process integration and modelling WP7 Transport and storage WP6 Scale up, economics, LCA WP8 Exploitation WP9 - Dissemination The CLEANKER project 23 23
24 Conclusions and Outlook Ca-LOOPING PROCESS INTEGRATION OPTIONS: 1. Cement plant-power plant coupling: Excellent expected performance Easily retrofittable with low cost Logistic problem: a very large power plant has to be built next to the cement plant 2. Post-combustion capture configuration: Low uncertainty in the feasibility of the process (very similar to application in power plants) Very high CO 2 capture expected Two calciners are present in the system, leading to high fuel consumptions 3. Integrated CaL configuration: High CO 2 capture efficiency without modifying rotary kiln operation (no need of kiln oxyfiring). Higher thermal efficiency and lower fuel consumptions expected (compared to option 2) New carbonator design and fluid-dynamic regime: fluid-dynamics, heat management and sorbent performance need validation
25 Thank you for your attention! Acknowledgement This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreements n. 641185 (Cemcap) and n. 764816 (Cleanker) www.sintef.no/cemcap Twitter: @CEMCAP_CO2 Disclaimer: The European Commission support for the production of this publication does not constitute endorsement of the contents which reflects the views only of the authors, and the Commission cannot be held responsible for any use which may be made of the information Technology contained therein for a better society