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

Chair CO2 – 01/12/ P 2 Agenda Post combustion. Chemical Looping. Oxy-combustion.

Chair CO2 – 01/12/ P 3 Post combustion Latest Advancements in Post Combustion CO 2 Capture Technology for Coal Fired Power Plant Steve Holton Mitsubishi Heavy Industry

Chair CO2 – 01/12/ P 4 Post combustion Mitsubishi Heavy Industry KS-1 TM solvent Steam consumption: *1.30 Ton Steam/Ton CO 2 *660 kcal/kg CO 2 Recovered Note: Steam 3 Bars G. Saturated Natural Gas flue gas CO 2 Recovery

Chair CO2 – 01/12/ P 5 Post combustion Mitsubishi Heavy Industry KS-1 TM solvent Increased CO 2 loading Steam consumption: *1.2 Ton Steam/Ton CO 2 *620 kcal/kg CO 2 Recovered Note: Steam 3 Bars G. Saturated Reduced, by 30% over MHI’s Conventional Process Further improvements Ton Steam/Ton CO 2 Natural Gas flue gas CO 2 Recovery

Chair CO2 – 01/12/ P 6 Post combustion Mitsubishi Heavy Industry  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 CO 2 capture: SO 2, SO 3,NO 2 Dust & particulates,Hydro carbons  Accumulation and effects of coal flue gas impurities for CO 2 Capture Plant have to be confirmed through long-term demonstration operation. Coal fired flue gas CO 2 Recovery  ~6,000 hrs were achieved at a commercial coal-fired power station in Southern Japan on a 10 ton/d for CO 2 Capture pilot  The MHI CO 2 Recovery process can be applied to the flue gas of coal-fired boilers

Chair CO2 – 01/12/ P 7 Post combustion Evaluation of a Hot Carbonate Absorption Process with High Pressure Stripping Enabled by Crystallization Shiaoguo Chen Carbon Capture Scientific LLC

Chair CO2 – 01/12/ P 8 Post combustion Hot Carbonate Absorption Process with High-Pressure Stripping Enabled by Crystallization HOT – CAP process flow diagram

Chair CO2 – 01/12/ P 9 Post combustion Hot Carbonate Absorption Process with High-Pressure Stripping Enabled by Crystallization Coal-fired flue gas CO 2 Recovery

Chair CO2 – 01/12/ P 10 Post combustion Hot Carbonate Absorption Process with High Pressure Stripping Enabled by Crystallization  High-stripping pressure low compression work low stripping heat (high CO 2 /H 2 O partial pressure ratio)  Low sensible heat Comparable working capacity than MEA Low Cp (~1/2)  Low heat of absorption 7-17 kcal/mol CO 2 (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 solvent degradation  Low-cost solvent  Less corrosiveness

Chair CO2 – 01/12/ P 11 Post combustion Concentrated Piperazine A Case Study of Advanced Amine Scrubbing Gary T. Rochelle The University of Texas at Austin

Chair CO2 – 01/12/ P 12 Post combustion Concentrated Piperazine A Case Study of Advanced Amine Scrubbing Process flow diagram W ideal = 113 kwh/tonne, W real = 219 kwh/tonne

Chair CO2 – 01/12/ P 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 CO 2  10-20% less energy than 30 wt% MEA Double the CO 2 mass transfer rate 1.8 x capacity Stripping at 150°C and atm  Superior Solvent management Thermally Stable Oxidatively stable Less volatile than 7 m MEA Good Opportunities for Reclaiming

Chair CO2 – 01/12/ P 14 Post combustion Post-Combustion CO 2 Capture Technology Pilot Performance and Scale-Up Analysis Phillip Boyle Powerspan Corp

Chair CO2 – 01/12/ P 15 Post combustion Post-Combustion CO 2 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 Improved performance.  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)

Chair CO2 – 01/12/ P 16 Post combustion Post-Combustion CO 2 Capture Technology Pilot Performance and Scale-Up Analysis  The steam extraction demand is 388,840 lbs/hr. Demands

Chair CO2 – 01/12/ P 17 Post combustion Post-Combustion CO 2 Capture Technology Pilot Performance and Scale-Up Analysis  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 CO 2 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. Impact on power plant efficiency

Chair CO2 – 01/12/ P 18 Post combustion Post-Combustion CO 2 Capture Technology Pilot Performance and Scale-Up Analysis Cost estimate and economic analysis

Chair CO2 – 01/12/ P 19 Post combustion Chilled Ammonia Field Pilot Program at We Energies Fred Kozak Alstom

Chair CO2 – 01/12/ P 20 Post combustion Chilled Ammonia Field Pilot Program at We Energies Simplified Process Schematic of the Chilled Ammonia Process (CAP) at We Energies 2NH 3 + H 2 O + CO 2 = (NH 4 ) 2 CO 3 (1) NH 3 + H 2 O + CO 2 = (NH 4 )HCO 3 (2) H 2 O + CO 2 + (NH 4 ) 2 CO 3 = 2(NH 4 )HCO 3 (3) (NH 4 )2CO 3 + NH 3 = NH 2 COONH 4 (4) SO 2 + 2NH 3 + H 2 O ⇒ (NH 4 ) 2 SO 3 (5) (NH 4 ) 2 SO 3 + 1/2O 2 ⇒ (NH 4 ) 2 SO 4 (6)

Chair CO2 – 01/12/ P 21 Post combustion Chilled Ammonia Field Pilot Program at We Energies Total Operating Hours Through Oct 2009 – 7717 The CO 2 capture efficiency ranged from 80 to 95%, with an average of 88.6% across the entire period CO 2 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. CO 2 capture efficiency and purity

Chair CO2 – 01/12/ P 22 Post combustion Chilled Ammonia Field Pilot Program at We Energies The average of five data points showed the CAP power requirement to be 200 kWh/ton of CO 2 delivered at 300 psig (21 bar(g)). Energy utilization 1210 kJ/kg

Chair CO2 – 01/12/ P 23 Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO 2 Capture Edward Levy Lehigh University

Chair CO2 – 01/12/ P 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

Chair CO2 – 01/12/ P 25 Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture LT turbine power loss CO 2 compressor power consumption

Chair CO2 – 01/12/ P 26 Post combustion Effects of Coal Type and Turbine Cycle Characteristics on Post-Combustion CO2 Capture LT turbine power loss Optimized extraction point 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 CO 2 compressor power An optimal extracting steam pressure from the LP turbine to operate the stripper reboiler minimizes the unit net power loss

Chair CO2 – 01/12/ P 27 Post combustion A new high-performance scrubbing agent for the separation of CO 2 from various gas streams Matthias Seiler EVONIK Degussa

Chair CO2 – 01/12/ P 28 Post combustion A new high-performance scrubbing agent for the separation of CO 2 from various gas streams 1. Presentation of a new high-performance CO 2 -absorbent made by Evonik Degussa 2. Performance characterization 3. Comparison with other state-of-the-art CO 2 absorbents

Chair CO2 – 01/12/ P 29 Post combustion A new high-performance scrubbing agent for the separation of CO 2 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

Chair CO2 – 01/12/ P 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

Chair CO2 – 01/12/ P 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.

Chair CO2 – 01/12/ P 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 Fe 3 O 4, an intermediate reduction product of Fe 2 O 3. TG examinations on pure Fe 2 O 3 indicate Fe 3 O 4 prevents the OC from further reduction to FeO. XRD analyses confirm the formation of Fe 3 O 4. Compared to the pure Fe 2 O 3 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 Fe 2 O 3.

Chair CO2 – 01/12/ P 33 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Carl Edberg Alstom power system

Chair CO2 – 01/12/ P 34 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration 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. Simplified scheme of the Oxy-Combustion principle

Chair CO2 – 01/12/ P 35 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration The main focus investigations for the oxy-combustion boiler

Chair CO2 – 01/12/ P 36 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration Results

Chair CO2 – 01/12/ P 37 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration 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 Dynamic process

Chair CO2 – 01/12/ P 38 Oxy-Combustion Oxy-Combustion Technology Development – Ready for Large Scale Demonstration 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 Schwarze Pumpe (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 CO 2 capture technology has been taken. Jänschwalde (Germany) is a priority site chosen by the Vattenfall Group for large-scale demonstration. Conclusions

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