Chemical Looping Technology

Transcription

1 Chemical Looping Technology by L. S. Fan Department of Chemical and Biomolecular Engineering The Ohio State University Columbus, Ohio U.S.A. ICEST June 2, 2014

2 Number of Publications with Chemical Looping in the Titles on Google Scholars Number of Publications Year

3 Combustion System

4 Gasification System Fly Ash By-Product Sulfur By-Product Slag By-Product IGCC Efficiency: 33% with CO 2 control Steigel and Ramezan, 2006

5 Chemical Looping Systems with CO 2 Generation or Separation Two typical types of looping reaction systems Oxygen Carrier (Type I) CO 2 Carrier (Type II) Me/MeO, MeS/MeSO 4 MeO/MeCO 3 1 st International Conference on Chemical Looping, Lyon, France, March (2010). 1 st Meeting of High Temperature Solids Looping 5 Cycle Network, Oviedo, Spain, September (2009).

6 Chemical Looping Systems with Non-CO 2 Generation Syngas CO + H 2 Chemicals H 2 O H 2 + O 2 chemical looping chemical looping chemical looping CH 4 or other Carbonaceous Fuels CH 4 or other Carbonaceous Fuels Solar Energy/ Nuclear Energy

7 CO 2 Capture from Fossil Energy Technological Solutions Source: José D. Figueroa, National Energy Technology Laboratory (NETL), USDOE

8 Comparison of OSU SYNGAS and Coal Direct Chemical Looping (CDCL) Processes with Traditional Coal to Hydrogen/Electricity Processes Overall Process Efficiency SCL Gasfication-WGS IGCC-SELEXOL Subcritical MEA Ultra-supercritical MEA Ultra-Supercritical Chilled Ammonia Syngas CLC H2 Membrane WGS CO2 Membrane WGS CDCL % Electricity Assumptions used are similar to those adopted by the USDOE baseline studies.

9 Exergy Analysis on Hydrogen Production Substance Enthalpy of degradation Exergy Exergy Rate (ε) Energy/Exery Loss Additional Energy Input Final Product Carbon kj/mol kj/mol 0 Heat Loss 48.8 kj Exergy Loss H 2 + CO Partial oxidation kj /Gasification kj ε = kj Heat Loss 36 kj Exergy Loss H 2 +CO kj Water Gas Shift kj ε = 0.82 I I. Contional Process Exergetic Efficiency 322.9/407.7 = 79.2% ε 1 Fe 3 O (0.395 mol) kj 71.9 kj ε = Fe kj Partial oxidation kj ε = kj Exergy Loss 77.8 kj thermal 380 K 12.41kJ Exergy H 2 + Fe 3 O kj kj ε = 0.82 II. Chemcial Looping Process Exergetic Efficiency 396.9/( )=94.5% ε = 0.16 II 9

10 Economics of Chemical Looping Process Water Coal Coal Prep. Existing equipment for repowering case Carrier Particle Makeup (Fe 2 O 3 ) CO 2 +H 2 O Reducer FeO/Fe Fe 2 O 3 Combustor Spent Air Steam Water Enhancer Gas Recycle Fan FGD HP Particulate Removal IP H 2 O Steam Cycle ID Fan CO 2 compressor LP FGD CO 2 Sequestration Stack Fly Ash and Carrier Particle Fines Electricity Base Plant MEA Plant CDCL Plant First-Year Capital ($/MWh) Fixed O&M ($/MWh) Coal ($/MWh) Variable O&M ($/MWh) TOTAL FIRST-YEAR COE ($/MWh) = +71% Air Existing equipment for repowering case ID Fan Pump Cooling Tower Existing equipment for repowering case = +33% Retrofit to conventional coal combustion process CDCL replaces existing PC boiler Additional equipment for CO 2 compression and transportation required Techno-Economic analysis performed comparing CDCL to Base Plant with no CO 2 capture and 90% CO 2 capture via post-combustion MEA process Thomas, T., L.-S. Fan, P. Gupta, and L. G. Velazquez-Vargas, Combustion Looping Using Composite Oxygen Carriers U.S. Patent No. 7,767,191 (2010, priority date 2003) The CDCL process can be also used for high efficient hydrogen production

11 Oxygen Carrier Particle Development Ellingham Diagram: Selection of Primary Metal

12 Force (N) Recyclability of Pure Fe 2 O 3 Recyclability of Composite Fe 2 O Cycle Pellet Reactivity 100 Cycle Pellet Strength Fresh 10 Cycles 100 Cycles

13 Structures of Iron Oxide FeO Fe 3 O 4 NaCl Type oxygen close-packed cubic pattern iron occupy all octahedral interstices inverse Spinel Type octahedral interstices 1/2 occupation rate tetrahedral interstices 1/8 occupation rate

14 Core-Shell Particle Formation through Cyclic Gas-Solid Reactions 4Fe (s) + 3O 2 (g) 2Fe 2 O 3 (s) (1) Fe 2 O 3 (s) + 3H 2 (g) 2Fe (s) + 3H 2 O (g) (2) If the cyclic reactions proceed through Fe cation diffusion, core-shell structure forms, e.g. Fe2O3 + Al2O3. If the cyclic reactions proceed through O anion diffusion, core-shell structure does not forms, e.g. Fe2O3 + TiO2. *Al2O3 is only a physical support, while TiO2 alters the solid-phase ionic diffusion mechanism

15 Fe2O3+Al2O3 VS Fe2O3+TiO2 after 50 redox cycles after 50 redox cycles

16 Evolution in Cyclic Binary Metal/Metal Oxide Systems: I. FeTi Original cross section Oxidation: cross section Oxidation: surface with platelets and whiskers EDS mapping of oxidized FeTi

17 Role of Support Oxidation of Fe and Fe/TiO 2 DFT Calculation Oxygen anion transfer in Wüstite and Ilemnite Energy barrier for O 2- can be reduced after support addition

18 Modes of CFB Chemical Looping Reactor Systems Mode 1- reducer: fluidized bed or co-current gas-solid (OC) flows Mode 2 - reducer: gas-solid (OC) countercurrent dense phase/moving bed flows Moving Bed Reducer CO 2 H 2 O Fluidized Bed Reducer CO 2, H 2 O Fuel Fuel Chalmers University CLC System OSU CLC System Thomas, T., L.-S. Fan, P. Gupta, and L. G. Velazquez-Vargas, Combustion Looping Using Composite Oxygen Carriers U.S. Patent No. 7,767,191 (2010) (priority date:2003).

19 FeO x FeO x CO 2 /H 2 O CO 2 /H 2 O Chemical Looping Reactor Design (x>y) Fluidized Bed v.s. Moving Bed FeO x FeO x CO 2 /H 2 O CO 2 /H 2 O 11.11% Maximum Solid Conversion 50.00% > U mfv Gas Velocity < U mfv (X>Y) Small 1.E+07 Particle Size Large (X>Y) FeO y CO/H 2 1.E+06 Fe 2 O 3 FeO y CO/H 2 1.E+05 Fluidized Bed Moving Bed 1.E+04 Fluidized Bed (x>y) Fe Moving Bed The Selected 3 O 4 Reactor Type 1.E+03 FeO y CO/H 2 1.E+02 FeO y CO/H 2 1.E+01 FeO 1.E+00 Fluidized Bed Moving Bed PCO2/PCO 1.E-01 Moving Bed Temperature (C) Fe 19

20 Particle Type Ni Cu Fe Type of Data Particle Type Lab Scale NiO/ MgAl 2 O 4 CFB 120 kw NiO/ MgAl 2 O 4 Lab Scale CFB 10kW Lab Scale kg/s or 14,000 36,000 ton/hour CFB 300W Moving Bed -H 2 25 kw CuO/ Fe 2 O 3 / Fe 2 O 3 / Al 2 O 3 CuO/Al 2 O 3 MgAl 2 O 4 Al 2 O 3 Composite Fe 2 O 3 Air Flow MWth and 10% Excess (mol/s) Volumetric Air Flow Rate at 1 atm and 900 ºC (m 3 /s) Particle Circulation 1000 MWth (kg/s) Reducer Solids Inventory (tonne) total Oxidizer Solids Inventory (tonne) n/a Total Medium Particle Size (μm) Particle Density (g/cm 3 ) Ut (m/s) Uc (m/s) Use (m/s) Typical Riser Superficial Gas Velocity (m/s) Bed Area Turbulent Section (if Required) at 1 atm (m 2 ) Bed Area Required for Riser Section at 1 atm (m 2 ) Corresponding Riser Diameter (m) Solids Flux at 1 atm (kg/m 2 s) Number of Beds Needed given 8 m ID Riser 3.23 <1 Number of Beds Needed given 1.5 m ID Riser Ug for a Single 1.5 m ID Riser at 1 atm (m/s) Ug for a Single 8 m ID riser at 1 atm (m/s) (Ug < Ut; N/A) Required Pressure for a Single 1.5m ID Riser (atm) Solids Flux for a Single 1.5 m ID Riser (kg/m 2 s) Required Pressure for a Single 8 m ID Riser (atm) 3.23 < 3,000 ton/hour Solids Flux for a Single 8 m ID Riser (kg/m 2 s) Ug < Ut; N/A

21 Scale OSU Chemical Looping Process Development Bench Scale Tests Sub-Pilot SCL Integrated Tests Particle Fixed Bed Tests Time

22 25 kw th OSU Sub-Pilot CDCL Demonstration for Coal Combustion Fully assembled and operational 500+ hours of operational experience 200+ hours continuous successful operation Smooth solid circulation Confirmed non-mechanical gas sealing under reactive conditions 13 test campaigns completed

23 Concentration (%) O2 Concentration (%) CO, CH4, CO2 Carbon Conversion (%) Concentration CO2 (%) Concentration CO, CH4, O2 (%) 200+ Hour Sub-Pilot Continuous Run - Sample Results Once-Through Reducer Carbon Conversion Profile 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Time of reaction (min) Continuous steady >90% carbon conversion from reducer throughout all solid fuel loading (5-25kW th ) <0.25% CO and CH 4 in reducer outlet = full fuel conversion to CO 2 /H 2 O <0.1% CO, CO 2, and CH 4 in combustor = negligible carbon carry over, nearly 100% carbon capture CDCL NO x /SO x Analysis Reducer Combustor SO x (ppm) NO X (lb/mmbtu) * ~ 0 *Conventional PC Boiler NO x Generation = lb/mmbtu 1 1. NETL. Cost and Performance Baseline for Fossil Energy Plants Volume 1 & 3b 100% 99% 98% 97% 96% 95% 94% 93% 92% 91% 90% Reducer Gas Concentration Profile CO Time (min) CH 4 CO CO2 CO CH4 Combustor Gas Concentration Profile 5% 5% 4% 4% 3% 3% 2% 2% 1% 1% 0% Time (min) CO2 O2 CO CH

24 Concentration (%) Concentration (%) 25 kw th OSU Sub-Pilot SCL Unit for Hydrogen Generation Recent Unit Demonstration 100 Reducer Gas Composition Over 300+ hours operation Average CO 2 purity generated throughout run > 99% >99.99% hydrogen purity at steady state Steady Pressure Profile throughout Test run H2 CO CO Differential Pressure Profile 0 8:52:48 AM 10:19:12 AM 11:45:36 AM 1:12:00 PM 100 Oxidizer Gas Composition 8 80 Pressure (" H20) DP2 DP3 DP H2 CO CO Hours 0 13:33:36 14:09:36 14:45:36 15:21:36

25 Concluding Remarks Chemical Looping embodies all elements of particle science and technology - particle synthesis, reactivity and mechanical properties, flow stability and contact mechanics, gas-solid reaction engineering OSU processes characterized by the moving bed reducer configuration are compact in design and high efficiency in operation. Success achieved in the operation of 200+ hour continuous sub-pilot CDCL run using coal and progress made in the on-going SYNGAS Chemical Looping pilot demonstration reflect the likelihood of commercialization of these technologies in the near future.

26 My Graduate Students and Research Associates Ted Thomas Himanshu Gupta Puneet Gupta Alissa Park Mahesh Iyer Luis Velazquez-Vargas Bartev Boghos Sakadjian Danny Wong Fanxing Li Shwetha Ramkumar FuChen Yu Fei Wang Liang Zeng Deepak Sridhar Ray Kim Dawei Wang Elena Chung Samuel Bayham Zhenchao Sun Mandar Kathe William Wang Songgeng Li Andrew Tong Nihar Phalak Siwei Luo Yao Wang Niranjani Deshpande Omar McGiveron Ankita Majumder

27 Industrial Collaborators Clear Skies: Bob Statnick B&W: Tom Flynn, Luis Vargas, Doug Devault, Bartev Sakadjian, Tom Flynn and Hamid Sarv CONSOL Energy: Dan Connell, Richard Winschel, and Steve Winberg Air Products: Robert Broekhuis, Bernard Toseland Shell/CRI: Tom Brownscombe PSRI: Reddy Kerry, Ted Knowlton and Ray Cocco