Process developments for CO 2 capture & valorization methods at CIEMAT

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1 Process developments for CO 2 capture & valorization methods at CIEMAT Josemaria Sánchez-Hervás, CIEMAT Combustion and Gasification Division Unit of Energy Valorisation of Fuels and Wastes Avenida Complutense Madrid (SPAIN) josemaria.sanchez@ciemat.es Symposium on Renewable Energy and Products from Biomass and Waste, CIUDEN 12&13 May 2015

2 Contents Brief presentation of CIEMAT Developments for CO 2 capture & valorization at CIEMAT Pre-combustion Post-combustion Oxy-combustion Conclusions List of Projects & Publications

3 CIEMAT Spanish Research Center in Energy, Environment and Technology Areas of activity: oenergy oenvironment otechnology oknowledge Transfer onational Lab for Fusion and Basic Research Staff : (Dec. 2013) Budget: 90 M / year Revenue: 44 M (2013)

4 ENERGY DEPARTMENT Combustion & Gasification Division Modelling Energy Valorisation of Fuels & Wastes Fuel Cells Combustion Gasification Gas Cleaning & Upgrading

5 CO 2 capture technologies

6 Developments for CO 2 capture & valorization at CIEMAT Approach 1: Pre-combustion CO 2 capture Study of the performance of WGS catalysts and CO 2 sorbents at laboratory scale under operating conditions that simulate a gasification plant. The effect of operating conditions is determined Pilot-scale evaluation of WGS catalysts, H 2 separation membranes, CO 2 capture sorbents Hybrid systems: Catalyst+Sorbent (Sorption-enhanced processes) (SE), Catalysts+Membrane, (Membrane reactor processes) (MR), Catalyst+Membrane+Sorbent (SEMR-processes)

WGS studies at laboratory scale & examples of results Study of sweet & sour WGS catalysts, commercial & synthesized WGS reaction: CO + H 2 O CO 2 + H 2 (ΔHº =-41 kj/mol) Effect of

7 WGS studies at laboratory scale & examples of results Study of sweet & sour WGS catalysts, commercial & synthesized WGS reaction: CO + H 2 O CO 2 + H 2 (ΔHº =-41 kj/mol) Effect of space velocity and steam to CO ratio on WGS activity of a Pt-based catalyst CO:44%, H 2 : 40%, CO 2 : 15%, CH 4 : 1% H 2 O/CO = 6, CO conversion (% v/v) h h h -1 Equilibrium Temperature (ºC) Activiy as a function of: -Pressure -Space velocity -Temperature -Gas composition -Steam/CO ratio CO conversion (%) M1, dry basis CO 44%, H 2, 40%, CO 2, 15%, CH 4, 1% P=10 bar GHSV=10000 h Temperature (ºC) H 2 O/CO=6,7 H 2 O/CO= 2

Pre-combustion carbon dioxide capture using regenerable sorbents for CO 2 capture in gasification processes (lab-scale)

saturation system mol/kg 6 4 MG61-K 2 CO 3 MG70-K 2 CO 3 2 MG30-K 2 CO 3 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.

8 Pre-combustion carbon dioxide capture using regenerable sorbents for CO 2 capture in gasification processes (lab-scale) Selection of solid sorbents in the T range (Sorption-enhanced, e.g. WGS) Sorption capacity as a function of P, T, steam Regeneration strategies Cyclic behaviour 10 8 Thermo balance and saturation system mol/kg 6 4 MG61-K 2 CO 3 MG70-K 2 CO 3 2 MG30-K 2 CO Hydrotalcites Micro-GC 1.0 P H2O 0.8 Materials: Dolomites, K-doped hydrotalcites, Doped with other ions (own development) Microactivity unit C/Co MG30-K 2 CO 3 35% H 2 O MG61-K 2 CO 3 35% H 2 O MG70-K 2 CO 3 35% H 2 O MG61-K 2 CO 3 dry gas t (min)

Test rig WGS & Pre-combustion CO 2 Capture (pilot-scale) TIA21 TIA23 TIA25 TIA27 TIA29 TIA22 TIA24 TIA26 TIA28 TIA30 Bench-Scale High

Temperature indicators Evaluation of the performance of the catalyst and sorbents under operating conditions which had proved successful

WGS tests 540 100 520 500 90 480 80 460 440 70 420 60 400 380 50 360 40 340 320 30 300 20 280 Sv = 4715 h-1 R = 3 260 10 240 0 0 30 60

9 Test rig WGS & Pre-combustion CO 2 Capture (pilot-scale) TIA21 TIA23 TIA25 TIA27 TIA29 TIA22 TIA24 TIA26 TIA28 TIA30 Bench-Scale High Temperature high-pressure Gas Treatment Plant: 20Nm3/h, 20 atm, 900ºC Incoloy 800H tubular reactor: D= 8 cm, h=1 m; 4-zone oven, 10 Temperature indicators Evaluation of the performance of the catalyst and sorbents under operating conditions which had proved successful at lab-scale Study of hybrid systems (catalyst + sorbent) SEWGS Temperature (ºC) CO conversion and temperature profile during one of the WGS tests Sv = 4715 h-1 R = Time (min) CO Conversion (% mol) TIA21 TIA22 TIA23 TIA24 TIA25 TIA26 TIA27 TIA28 TIA29 TIA30 TIA31 CO Conversion

10 Selective membranes for H 2 /CO 2 separation Dense or non-porous palladium membranes, the transport mechanism relies on the principle of solution/diffusion through the bulk of the material Highly selective

H 2 /CO 2 separation by membranes (pilot-scale) Bench-scale facility: 2 Nm 3 /h, T

nse Pd layer over porous SS support; Tubular O.D.

systems: Membrane + catalysts (WGSMR) Development of membranes (ternary alloys) Effect

H 2 /CO 2 /H 2 O (32.67/33.54/33.79) H2/CO2 H 2 2 (41.80/58.20) (41.89/43.00/15.

88) HH2/CO2 2 2 (50/50) (50/50) FBR H2/CO2 (50/50) Mixture 1: 41.8 % H2 Mixture 2: 17.

11 H 2 /CO 2 separation by membranes (pilot-scale) Bench-scale facility: 2 Nm 3 /h, T 600ºC and up to 12 bar Membrane: Dense Pd layer over porous SS support; Tubular O.D. =2,54 cm; L= 15 cm Permeation studies; Effect of P, T, GHSV, componentes Hybrid systems: Membrane + catalysts (WGSMR) Development of membranes (ternary alloys) Effect of CO 2 content on HR and JH 2 for H 2 /N 2 /CO 2 mixtures HR [%] H 2 /CO 2 /H 2 O (32.67/33.54/33.79) H2/CO2 H 2 2 (41.80/58.20) (41.89/43.00/15.11) (45.22/46.42/8.36) (46.39/47.62/5.99) (46.44/47.68/5.88) HH2/CO2 2 2 (50/50) (50/50) FBR H2/CO2 (50/50) Mixture 1: 41.8 % H2 Mixture 2: 17.2 % H2 CO 2 [% v./v.] HR and CO 2 conversion in different ternary mixtures of H 2 /CO 2 /H 2 O [%] HR CO2 conversion J H2 [mol/m 2.s]

Hybrid Systems SEWGS WGSMR CO conversion enhancement due to removing hydrogen or carbon dioxide from the reaction environment Space velocity, T, and steam to CO ratio values which would not fully

120 110 100 90 80 70 60 50 40 30 20 T =380ºC, F feed gas =10.93 Nl/min; GHSV=16771 h -1 ; R (H 2 O/CO)=3; Feed Gas composition (d.b.

12 Hybrid Systems SEWGS WGSMR CO conversion enhancement due to removing hydrogen or carbon dioxide from the reaction environment Space velocity, T, and steam to CO ratio values which would not fully convert CO into CO 2 and H 2 WGS reaction: CO+H 2 O=H 2 +CO 2 SEWGS WGSMR Performance of a HTC CO 2 capture sorbent at bench scale under sweet WGS operating conditions H 2 permeate flow-rate (ml/min) T =380ºC, F feed gas =10.93 Nl/min; GHSV=16771 h -1 ; R (H 2 O/CO)=3; Feed Gas composition (d.b.)=44% v/v CO, 40% v/v H 2, 16%v/v CO 2 Enhacement of CO conversion due to H 2 removal Fixed bed conversion 10 H 2 permeate flow-rate (ml/min) 10 0 X CO (% vol) Feed side pressure (bar a) CO conversion x CO (% vol) Results of WGSMR studies

13 Developments for CO 2 capture & valorization at CIEMAT Approach 2: Post-combustion CO 2 capture Assessment of CO 2 capture by conventional or electropromoted adsorption at lab- and benchscale under realistic conditions Assessment at bench-scale of Electropromoted CO 2 valorisation into clean fuels

Regeneration capacity Difference of temperatures between adsorption and

14 Post-combustion CO 2 capture by physical adsorption Targets for selection of adsorbents High CO 2 adsorption capacity High selectivity Regeneration capacity Difference of temperatures between adsorption and desorption as small as possible Operational in the ºC temperature window

Post-combustion CO 2 capture by physical adsorption Test rig Net CO 2 capture capacity for different sorbents Net CO 2 capture capacity (mg CO 2/ g adsorbent) 140 120 100 80

ZEOLITE CO 2 +N 2 Up to 20 Nm 3 /h combustion off-gases, 500ºC, atmosp.

15 Post-combustion CO 2 capture by physical adsorption Test rig Net CO 2 capture capacity for different sorbents Net CO 2 capture capacity (mg CO 2/ g adsorbent) activated alumina active carbon zeolite CO 2 exit concentration< 1%v/v Cycle number Breakthrough curves under the different 1,0gas composition 0,8 FRESH ZEOLITE CO 2 +N 2 Up to 20 Nm 3 /h combustion off-gases, 500ºC, atmosp. Pressure, FTIR analyzer Exiting CO 2 (%) 0,6 0,4 0,2 CO 2 +H 2 O+N 2 CO 2 +H 2 O+O 2 +SO 2 +N 2 CO 2 +H 2 O+O 2 +SO 2 +NO+N 2 0,0 27mg/g 54mg/g 70 mg/g 134 mg/g Time (sec) Sorbent: Zeolite, Adsorption T 47ºC, Space velocity 0,88 Nl h-1 g-1

Electrochemical Promotion of Catalysis (EPOC) for CO 2 capture and conversion into clean fuels Non-Faradaic electrochemical modification of catalytic activity (NEMCA effect) or electrochemical

16 Electrochemical Promotion of Catalysis (EPOC) for CO 2 capture and conversion into clean fuels Non-Faradaic electrochemical modification of catalytic activity (NEMCA effect) or electrochemical promotion The catalytic activity and selectivity of metal films deposited on solid electrolytes can be altered dramatically and reversibly by applying an electrical current or potential between the metal catalyst film and a second film (counter electrode) also deposited on the solid electrolyte

17 Electrochemical Promotion of Catalysis (EPOC) for CO 2 capture and conversion into clean fuels

18 Electrochemical Promotion of Catalysis (EPOC) for CO 2 capture and conversion into clean fuels Design and development of catalysts (tube, candle, monolith), (Dip-coating, electroless, painting): K- βal 2 O 3 /YSZ, Reference-counter electrode Au, Catalyst electrode Pt, Ni, Cu.. Characterisation (SEM-EDX, XRD, XÇPS, Voltammetry) Electrochemical CO 2 capture: Effect of T, gas composition; electrochemical desorption Electrochemical hidrogenation of CO 2 Micro-GC, NDIR CO 2 /CO TCD-H2 CO2 /Selectivity to CH 3 OH/C 2 H 5 OH (%) CO 2 rco rco promoted 2 unpromoted 2 Selectivity to CH 3 OH Selectivity to C 2 H 5 OH Potential (V)

19 Developments for CO 2 capture & valorization at CIEMAT Approach 3: Oxy-combustion Fuel and waste valorization by means of oxycombustion Emissions minimization, CO 2 capture and fate of pollutants and trace elements (e.g. Hg) under oxycombustion conditions

20 Oxyfuel lab-scale Reactor Ash deposition behaviour Slagging, fouling and corrosion issues Sorbents for Hg retention

5 kwt OXYFUEL BFB PILOT PLANT 1000 TI-04 TI-05 TI-06 Caudal_O2 Caudal_CO2 condiciones oxicombustión 100 Alimentación carbón Temperatura (ºC) 800 600 400 200 CO 2 80 60 40 20 Caudal O2, CO2

21 5 kwt OXYFUEL BFB PILOT PLANT 1000 TI-04 TI-05 TI-06 Caudal_O2 Caudal_CO2 condiciones oxicombustión 100 Alimentación carbón Temperatura (ºC) CO Caudal O2, CO2 (l/min) Tiempo (h) O 2 0 Combustion behaviour: fuel, T, O 2, gas recirculation Emission formation: SO 2, NOx, N 2 O The fate of trace metals in solid and gas phase, emphasis on Hg

22 Conclusions CIEMAT is engaged in the development of technologies for pre- post- and oxycombustion CO 2 capture. Developments include: Pre combustion: WGS catalysts, Membranes for H 2 separation, sorbents for CO2 capture. Hybrid systems (sorption enhanced membranereactorassisted) Post combustion: Sorbents for CO 2 capture and electrochemical promotion of catalysis Oxy combustion: Fuel and waste valorization, release of pollutants and trace elements Developments are based on experimental assessment at laboratory and bench-scale Open to collaboration in R&D competitive calls and offer of technical services

23 List of Projects INNPACTO BIOH2 New Strategies for Exploitation of Biomass for Sustainable Production of Hydrogen without CO 2 Release MINECO, IPT , FECUNDUS: Advanced concepts and process schemes for CO 2 -free fluidised and entrained bed co-gasification of coals, RFCS, RFCR-CT , CAPHIGAS: Development of a hybrid system WGS-sorbent-membrane for CO 2 capture with H 2 production in gasification processes, MICINN, ENE , PSE-CO2: Singular and Strategic Project of Advanced Technologies of CO 2 capture and storage: SP1 Precombustion CO2 capture (PSE ) MEC, PROMOCAP Development and Study of Electrochemical Promotion Systems for CO 2 Capture and Valorization in Combustion Gases, MICINN, ENE , CENIT CO2, National Strategic Consortium for CO 2 technical research WP4 Postcombustion CO 2 Capture, MINER-CDTI,

24 Further info-publications Pre-combustion CO 2 capture Experimental studies of CO 2 capture by a hybrid catalyst/adsorbent system applicable to IGCC processes M. Maroño, Y. Torreiro, D. Cillero, J.M. Sánchez, Applied Thermal Engineering, Applied Thermal Engineering, Volume 74, 5 January 2015, Hydrogen separation studies in a membrane reactor system: Influence of feed gas flow rate, temperature and concentration of the feed gases on hydrogen permeation M.M. Barreiro, M. Maroño, J.M. Sánchez, Applied Thermal Engineering, Volume 74, 5 January 2015, Synthesis of copper promoted high temperature water-gas shift catalysts by oxidationprecipitation J. Dufour, C. Martos, A. Ruiz, M. Maroño, J.M. Sánchez, International Journal of Hydrogen Energy, Volume 39, Issue 31, 22 October 2014, Pages Performance of a hybrid system sorbent catalyst membrane for CO 2 capture and H 2 production under pre-combustion operating conditions M. Maroño, M.M. Barreiro, Y. Torreiro, J.M. Sánchez, Catalysis Today 236 (2014) Lab-scale tests of different materials for the selection of suitable sorbents for CO 2 capture with H 2 production in IGCC processes Marta Maroño, Yarima Torreiro, Lucía Montenegro, José María Sánchez, Fuel 116 (2014) Bench-scale study of separation of hydrogen from gasification gases using a palladiumbased membrane reactor, J.M. Sánchez, M.M. Barreiro, M. Maroño, Fuel 116 (2014) Hydrogen permeation through a Pd-based membrane and RWGS conversion in H 2 /CO 2, H 2 /N 2 /CO 2 and H 2 /H 2 O/CO 2 mixtures, M.M. Barreiro, M. Maroño, J.M. Sánchez, International Journal of Hydrogen Energy, (2014) 39, 9,

25 Further info-publications Pre-combustion CO 2 capture (cont.) Laboratory- and bench-scale studies of a sweet water gas-shift catalyst for H2 and CO2 production in pre-combustion CO2 capture J.M. Sánchez, M. Maroño, D. Cillero, L. Montenegro, E. Ruiz, (2013), Fuel, 114, , December 2013, CF 1H011, CF1H212. Influence of steam partial pressures in the CO2 capture capacity of K-doped hydrotalcite-based sorbents for their application to SEWGS processes Marta Maroño, Yarima Torreiro, Luis Gutierrez; International Journal of Greenhouse Gas Control, Volume 14, May 2013, Pages Water Gas Shift and Membrane Reactor Studies for the Production of a Hydrogen-rich Stream M. Maroño, J.M. Sánchez. In: Gasification: Chemistry, Processes and Applications, Chapter 2 pp Energy Science, Engineering and Technology Series, Editor Michael D. Baker, Nova Science Publishers, Inc. New York; ISBN Hydrogen enrichment and separation from synthesis gas by the use of a membrane reactor J.M. Sánchez, M.M. Barreiro, M. Maroño, Biomass and Bionenergy 35 (2011) S132-S144

26 Further info-publications Post- & Oxy-combustion CO 2 capture Electrochemical synthesis of fuels by CO 2 hydrogenation on Cu in a potassium ion conducting membrane reactor at bench scale E. Ruiz, D. Cillero, P.J. Martínez, A. Morales, G. San Vicente, G. de Diego, J.M. Sánchez, Catalysis Today 236 (2014) Bench-scale study of electrochemically assisted catalytic CO 2 hydrogenation to hydrocarbon fuels on Pt, Ni and Pd films deposited on YSZ, E. Ruiz, D. Cillero, P.J. Martínez, A. Morales, G. San Vicente, G. de Diego, J.M. Sánchez, Journal of CO 2 Utilization, Volume 8, December 2014, 1 20 Bench scale study of electrochemically promoted CO 2 capture on Pt/K-βAl 2 O 3,E.Ruiz, D. Cillero, A. Morales, G. San Vicente, G. de Diego, P.J. Martínez, J.M. Sánchez, (2013), Electrochimica Acta, 112, CO 2 capture from PCC power plants using solid sorbents: Bench scale study on synthetic gas E. Ruiz, J.M. Sánchez, M. Maroño, J. Otero (2013), Fuel, 114, Bench scale study of electrochemically promoted catalytic CO2 hydrogenation to renewable fuels E. Ruiz, D. Cillero, P.J. Martínez, A. Morales, G. San Vicente, G. de Diego, J.M. Sánchez, (2013), Catalysis Today, 210, Trace metals removal through a catalytic hybrid filter during co-firing of different biomass waste materials, M.L. Contreras, F.J. García-Frutos, R. Ramos, D. Sanz, A. Bahillo, Fuel 150 (2015) Oxyfuel combustion effects on trace metals behavior by equilibrium calculations, M.L. Contreras, F.J. García-Frutos, A. Bahillo, Fuel 108 (2013) Study of the combustion behaviour of coal-biomass blending during oxy-fuel combustion by thermogravimetric analysis, Submitted for publication in JTAC

27 THANK YOU VERY MUCH FOR YOUR ATTENTION Any Questions?

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