Modelling study of two chemical looping reforming reactor configurations: Looping vs. switching

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Engineering Conferences International ECI Digital Archives Fluidization XV Proceedings 5-23-2016 Modelling study of two chemical looping reforming reactor configurations: Looping vs. switching Joana F. Morgado University of Coimbra,Portugal ; Norwegian University of Science and Technology, Norway, joana.f.morgado@sintef.no Schalk Cloete SINTEF Materials and Chemistry, Flow Technology Department, Norway John Morud SINTEF Materials and Chemistry, Flow Technology Department, Norway Thomas Gurker ANDRITZ AG, Austria Shahriar Amini SINTEF Materials and Chemistry, Flow Technology Department, Norway Follow this and additional works at: http://dc.engconfintl.org/fluidization_xv Part of the Chemical Engineering Commons Recommended Citation Joana F. Morgado, Schalk Cloete, John Morud, Thomas Gurker, and Shahriar Amini, "Modelling study of two chemical looping reforming reactor configurations: Looping vs. switching" in "Fluidization XV", Jamal Chaouki, Ecole Polytechnique de Montreal, Canada Franco Berruti, Wewstern University, Canada Xiaotao Bi, UBC, Canada Ray Cocco, PSRI Inc. USA Eds, ECI Symposium Series, (2016). http://dc.engconfintl.org/fluidization_xv/33 This Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in Fluidization XV by an authorized administrator of ECI Digital Archives. For more information, please contact franco@bepress.com.

Modelling study of two Chemical Looping Reforming reactor configurations: Looping vs. Switching Joana Francisco Morgado 2,3, Schalk Cloete 1, John Morud 1, Thomas Gurker 4 Rosa M. Quinta-Ferreira 3, Shahriar Amini 1 * 1 SINTEF Materials and Chemistry, Flow Technology Department, Norway 2 Norwegian University of Science and Technology, Dept. of Energy and Process Engineering, Norway 3 University of Coimbra, Dept. of Chemical Engineering, Portugal 4 ANDRITZ AG GmbH, Austria Presenter e-mail: joana.f.morgado@ntnu.no Montebello, 23 May 2016

Outline 1. Objective 2. CLR vs. GSR principles 3. Simulations 4. Results and discussion 5. Conclusions 2

2. Objective of the work To compare the performance of two precombustion reactor concepts Chemical Looping Reforming (CLR) Gas Switching Reforming (GSR) 3

3. CLR vs. GSR CLR Two interconnected FBR reactors (AR and FR); OC continuously transported between AR and FR; No mixing between N 2 and fuel; Scale-up and operational challenges. GSR One FBR for oxidation and reduction of the OC switching concept; Alternating feed of air and fuel to the reactor unit; Undesired mixing between N 2 and fuel; Facilitates scaling-up under pressurized conditions. 4

4. Simulations 1-D phenomenological model for FBR Single formulation is used! Generic formulation based on the generic model developed by Abba et al. (2003) [1] ; Uses an averaging probabilistic approach by Thompson et al. (1999) [2] ; Two-phase model by Toomey and Johnstone (L- and H-phases) [3,4] ; Differential Balances Mass balance Gas total mass balance Gas species mass balance for each phase Total solids species mass balance Total Energy balance Pressure Balance Numerical scheme: Method of lines (MATLAB routine ode15s) Finite volume method (discretization in space) Non-uniform grid Convective term: 1 st order upwind scheme Diffusion term: central differences scheme 1. Abba, I.a., et al., Spanning the flow regimes: Generic fluidized-bed reactor model. AIChE Journal, 2003. 49: p. 1838-1848. 2. Thompson, M.L., H. Bi, and J.R. Grace, A generalized bubbling / turbulent fuidized-bed reactor model. Chemical Engineering Science, 1999. 54: p. 3-10. 3. Kunii, D. and O. Levenspiel, Fluidization Engineering. second ed. 1991: Butterworth-Heinemann. 4. Mahecha-Botero, A., et al., Pure hydrogen generation in a fluidized bed membrane reactor: Application of the generalized comprehensive reactor model. Chemical Engineering Science, 2009. 64(17): p. 3826-3846. 5

4. Simulations Reforming stage Reactions and Kinetics Reforming[1] Ni as catalyst Oxidation of the oxygen carrier [2] CH 4 + H 2 O CO + 3H 2 Ni + 1 2 O 2 NiO CO + H 2 O CO 2 + H 2 CH 4 + 2H 2 O CO 2 + 4H 2 Air Reactor Fuel Reactor Oxidation stage Reduction of the oxygen carrier [2] CH 4 + 4NiO 4Ni + CO 2 + 2H 2 O H 2 + NiO Ni + H 2 O CO + NiO CO 2 + Ni Reduction stage CLR GSR 1. Xu, J. and G.F. Froment, Methane steam reforming, methanation and water-gas shift: I. Intrinsic kinetics. AIChE Journal, 1989. 35(1): p. 88-96. 2. Abad, A., et al., Mapping of the range of operational conditions for Cu-, Fe-, and Ni-based oxygen carriers in chemical-looping combustion. Chemical Engineering Science, 2007. 62(1-2): p. 533-549. 6

4. Simulations Simulation Parameters How to compare these two technologies? Same simulation parameters and physical properties Study variable: Degree of Oxygen Carrier utilization How to adjust this parameter? 7

4. Simulations CLR: Oxygen carrier flux OC flux: OC residence time GSR: Cycle time flux cycle time: reduction + oxidation Higher oxygen carrier conversion CLR GSR Degree of OC utilization (%) OC flux (kg/m 2 s) Oxidation stage time (s) Reduction stage time (s) Reforming stage time (s) 10 466 25 13 25 20 233 68 34 68 40 116.5 198 99 198 60 82.4 400 200 400 80 58.25 - - - 8

5. Results: Profiles Chemical Looping Reforming: Fuel Reactor Reforming reactions dominate at the beginning of the reactor system far from equilibrium conditions production of H 2 density decrease Reduction reactions dominate at the end; Low amount of NiO through the bed; Temperature almost constant good axial mixing Maximum values: 2.94 kg/m3 for the gas density, 1 for the void fraction, 2.4 m/s for the superficial velocity and 989 C for the temperature 9

5. Results Gas Switching Reforming O 2 totally consumed in the oxidation stage; Undesired mixture of N 2 with fuel reduces CO 2 capture performance; 1 2 3 1. Oxidation 2. Reduction 3. Reforming 10

5. Results Performance Measures CH 4 conversion CO selectivity H 2 production performance CLR GSR Higher OC utilization Lower reduction temperature low CH 4 conversion (by reforming endothermic reactions) productivity of H 2 decreases Lower CO selectivity WGS reaction Lower OC utilization Lower CO selectivity To supply heat Higher OC utilization Lower CH 4 conversion Reforming stage is higher Lower H 2 productivity lower CH 4 conversion Lower OC utilization Higher amount of N 2 mixed with fuel Short cycle times 11

6. Conclusions 1. CLR Lower degree of OC utilization (higher OC circulation rate) higher temperature in fuel reactor better reforming performance However, high OC circulation rate can bring practical and economic challenges 2. GSR Lower degree of OC utilization (shorter stage times) higher temperature in reforming stage higher CH 4 conversion and H 2 production However, undesired mixing of N 2 with CO 2 and syngas increases with shorter stage times 12

6. Conclusions 3. CLR vs. GSR H 2 production and CO conversion is higher in GSR Fuel conversion is higher for CLR with higher CO 2 content CLR is best suited to thermal power production with pre-combustion CO 2 capture and GSR to pure H 2 production 13

Thank you for your Patience!!! Questions? 14