9 th Annual CCS Conference Pittsburgh Pennsylvania May 10-13 2010

1. 9th Annual CCS Conference Pittsburgh Pennsylvania May 10-13 2010 Y. Riachi, D.Clodic CTSC Chaire Paris, 01/12/2010

2. Agenda • Post combustion. • Chemical Looping. • Oxy-combustion.

3. Post combustion Latest Advancements in Post Combustion CO2 Capture Technology for Coal Fired Power Plant Steve Holton Mitsubishi HeavyIndustry

4. Post combustion Mitsubishi Heavy Industry Natural Gas flue gas CO2Recovery • KS-1TMsolvent • Steam consumption: • *1.30 Ton Steam/Ton CO2 • *660 kcal/kg CO2 Recovered • Note: Steam 3 Bars G. Saturated

5. Post combustion Mitsubishi Heavy Industry Natural Gas flue gas CO2Recovery • KS-1TMsolvent • Increased CO2loading • Steam consumption: • *1.2 Ton Steam/Ton CO2 • *620 kcal/kg CO2 Recovered • Note: Steam 3 Bars G. Saturated • Reduced, by 30% over MHI’s Conventional Process • Further improvements 0.85 - 1 Ton Steam/Ton CO2

6. Post combustion Mitsubishi Heavy Industry Coal fired flue gas CO2Recovery • Impurities in the Coal Fired Flue Gas depend on coal type and flue gas treatment conditions and should be clarified. • The following impurities have to be carefully treated before CO2 capture: SO2, SO3 ,NO2Dust & particulates ,Hydro carbons • Accumulation and effects of coal flue gas impurities for CO2 Capture Plant have to be confirmed through long-term demonstration operation. • ~6,000 hrs were achieved at a commercial coal-fired power station in Southern Japan on a 10 ton/d for CO2 Capture pilot • The MHI CO2 Recovery process can be applied to the flue gas of coal-fired boilers

7. Post combustion Evaluation of a Hot Carbonate Absorption Process with High Pressure Stripping Enabled by Crystallization Shiaoguo Chen Carbon Capture Scientific LLC

8. Post combustion Hot Carbonate Absorption Process with High-Pressure Stripping Enabled by Crystallization HOT – CAP process flow diagram

9. Post combustion Hot Carbonate Absorption Process with High-Pressure Stripping Enabled by Crystallization Coal-firedflue gas CO2Recovery

10. Post combustion Hot Carbonate Absorption Process with High Pressure Stripping Enabled by Crystallization • High-stripping pressure • low compression work • low stripping heat (high CO2/H2O partial pressure ratio) • Low sensible heat • Comparable working capacity than MEA • Low Cp (~1/2) • Low heat of absorption • 7-17 kcal/mol CO2(heat of crystallization incld.) vs. 21 kcal/mol for MEA • Kinetics improved by employing high-concentration PC and high-absorption temperature • FGD may be eliminated • No solventdegradation • Low-costsolvent • Lesscorrosiveness

11. Post combustion Concentrated Piperazine A Case Study of Advanced Amine Scrubbing Gary T. Rochelle The University of Texas at Austin

12. Post combustion Concentrated Piperazine A Case Study of Advanced Amine Scrubbing Process flow diagram Wideal = 113 kwh/tonne, Wreal = 219 kwh/tonne

13. Post combustion Concentrated Piperazine A Case Study of Advanced Amine Scrubbing Conclusions • A published amine that requires only 2.6 MJt or 220 kwhe /tonne CO2 • 10-20% less energy than 30 wt% MEA • Double the CO2 mass transfer rate • 1.8 x capacity • Stripping at 150°C and 11-17 atm • Superior Solvent management Thermally Stable • Oxidatively stable • Less volatile than 7 m MEA • Good Opportunities for Reclaiming

14. Post combustion Post-Combustion CO2 Capture Technology Pilot Performance and Scale-Up Analysis Phillip Boyle PowerspanCorp

15. Post combustion Post-Combustion CO2 Capture Technology Pilot Performance and Scale-Up Analysis • 2008 • Powerspan Corp. has been testing its post-combustion • ECO2® carbon capture technology. • 1-MWe pilot facility located at First Energy's R.E. Burger Plant near Shadyside, Ohio. • 2009 • Enhancements to the pilot configuration and solvent chemistry • Improvedperformance. • 2010 • Assessment of the design, operation, and performance of the ECO2 pilot, • Implications of test results from the ECO2 pilot for new and retrofitted coal-fired power plants (200 MW and larger units)

16. Post combustion Post-Combustion CO2 Capture Technology Pilot Performance and Scale-Up Analysis Demands • The steam extraction demand • is 388,840 lbs/hr.

17. Post combustion Post-Combustion CO2 Capture Technology Pilot Performance and Scale-Up Analysis Impact on power plant efficiency • Subcritical • The net output of the plant is reduced by about 30%, • The plant net efficiency is reduced by 9.97%. • Supercritical • The contribution of the LP turbine section to total power generation in a subcritical steam cycle is relatively high compared to the corresponding contribution in a supercritical steam cycle. • The extraction of LP steam prior to the LP turbine results in a higher percentage of power loss for a subcritical unit than would be the case for a supercritical unit. • The higher CO2 production per MWh for the subcritical case requires more steam for regeneration and more electrical power for compression than would occur for a more efficient plant.

18. Post combustion Post-Combustion CO2 Capture Technology Pilot Performance and Scale-Up Analysis Costestimate and economicanalysis

19. Post combustion Chilled Ammonia Field Pilot Program at We Energies Fred Kozak Alstom

20. Post combustion Chilled Ammonia Field Pilot Program at We Energies Simplified Process Schematic of the Chilled Ammonia Process (CAP) at We Energies 2NH3 + H2O + CO2 = (NH4)2CO3 (1) NH3 + H2O + CO2 = (NH4)HCO3 (2) H2O + CO2 + (NH4)2CO3 = 2(NH4)HCO3 (3) SO2 + 2NH3 + H2O ⇒ (NH4)2 SO3 (5) (NH4)2SO3 + 1/2O2 ⇒ (NH4)2SO4 (6) (NH4)2CO3 + NH3 = NH2COONH4 (4)

21. Post combustion Chilled Ammonia Field Pilot Program at We Energies CO2 capture efficiency and purity • Total Operating Hours Through Oct 2009 – 7717 • The CO2 capture efficiency ranged from 80 to 95%, with an average of 88.6% across the entire period • CO2 purity is consistently above 99% with a moisture content in the range of 2,000 to 4,000 ppmv and an ammonia content of less than 10 ppmv.

22. Post combustion Chilled Ammonia Field Pilot Program at We Energies Energy utilization 1210 kJ/kg • The average of five data points showed the CAP power requirement to be 200 kWh/ton of CO2 delivered at 300 psig (21 bar(g)).

23. Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture Edward Levy Lehigh University

24. Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture Effect of Coal type and steam cycle on unit performances • Steam cycle • Subcritical cycle • Supercritical cycle • Coal type • Bituminous • PRB

25. Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture LT turbine power loss CO2 compressor power consumption

26. Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture Optimized extraction point LT turbine power loss • Lower steam pressure and temperature at the steam extraction point, reduces the turbine power loss • Reducing stripper pressure level increases the heat needed for solvent regeneration and CO2 compressor power • An optimal extracting steam pressure from the LP turbine to operate the stripper reboiler minimizes the unit net power loss

27. Post combustion A new high-performance scrubbing agent for the separation of CO2 from various gas streams Matthias Seiler EVONIK Degussa

28. Post combustion A new high-performance scrubbing agent for the separation of CO2 from various gas streams • 1. Presentation of a new high-performance CO2 -absorbent made by Evonik Degussa • 2. Performance characterization • 3. Comparison with other state-of-the-art CO2 absorbents

29. Post combustion A new high-performance scrubbing agent for the separation of CO2 from various gas streams • Absorption capacity of Evonik absorbent 1.7 times betterthan MEA • Cyclic capacity of Evonik absorbent 1.7 –2.4 times betterthan MEA • Corrosion for Evonik absorbent Factor 10 better/ lower than for MEA • Absorption kinetics of Evonik absorbent as good as MEA • Absorption enthalpy of Evonik absorbent 50% better/ lower than MEA • Viscosity of Evonik absorbent comparable to MEA • Chemical stability of Evonik absorbent appropriate • Volatility of Evonik absorbent better/ lower than MEA

30. Chemical looping Water Vapor Impact on Oxygen Carrier Performance for Chemical Looping Combustion of Solid Fuels University of Kentucky, Center for Applied Energy Research

31. Chemical looping Water Vapor Impact on Oxygen Carrier Performance for Chemical Looping Combustion of Solid Fuels • Water vapor improves the rate and completeness of direct char combustion with OCs by facilitating in-situ gasification. • The influence of OC particle size on direct char combustion process was also examined by thermogravimetric analysis. The results show no significant difference among the five size ranges.

32. Chemical looping Water Vapor Impact on Oxygen Carrier Performance for Chemical Looping Combustion of Solid Fuels • The results obtained from OC reductions in simulated syngas with and without adding 10% water vapor at 950°C show that the presence of water vapor causes reduction of OC performance in terms of oxygen carrying capacity and reactivity due to the formation of Fe3O4, an intermediate reduction product of Fe2O3. • TG examinations on pure Fe2O3 indicate Fe3O4 prevents the OC from further reduction to FeO. XRD analyses confirm the formation of Fe3O4. • Compared to the pure Fe2O3 powders, some of the freeze-granulated OCs show better resistance towards the water vapor effect possibly because the porous alumina supports provide better access of reactive gases to Fe2O3.

33. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Carl Edberg Alstom power system

34. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Simplified scheme of the Oxy-Combustion principle The combustion of the fuel in a mixture of recirculated flue gas and almost pure oxygen results in changes in the combustion behavior as well as in the combustion products, which have some effects on the design of a boiler.

35. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration The main focus investigations for the oxy-combustion boiler

36. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Results

37. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Dynamic process • Typical periods of time for standard procedures: • Venting of boiler and flue gas paths: approx. 20 minutes • Start of fire up to full load: approx. 45 minutes • Switch from air to oxy-combustion mode: approx. 20 - 30

38. Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Conclusions • The post-combustion and oxy-combustion technology will be available commercially in 2015 for large scale plants (e.g. 800 MWe). • Results from the Vattenfall’s 30 MWth oxy-combustion pilot in SchwarzePumpe (Germany) and the Alstom’s 15 MWth oxy-combustion pilot (BSF) in Windsor (USA) are very encouraging and support the commercial viability of the oxy-combustion technologies. • With a feasibility study executed by Vattenfall and recently completed with the involvement of Alstom, a decisive step towards industrial implementation of CO2 capture technology has been taken. • Jänschwalde (Germany) is a priority site chosen by the Vattenfall Group for large-scale demonstration.

39. Merci pour votre attention