Challenges to Demonstration Review of Technology Development Beyond the Oxyfuel Combustion Boiler

Challenges to Demonstration Review of Technology Development Beyond the Oxyfuel Combustion Boiler Stanley Santos IEA Greenhouse Gas R&D Programme 39 th IFRF TOTEM & RELSCOM Workshop Pisa, Italy 18 June 2013

IEA Greenhouse Gas R&D Programme A collaborative research programme founded in 1991 Aim: Provide members with definitive information on the role that technology can play in reducing greenhouse gas emissions. Producing information that is: Objective, trustworthy, independent Policy relevant but NOT policy prescriptive Reviewed by external Expert Reviewers Subject to review of policy implications by Members IEA GHG is an IEA Implementing Agreement in which the Participants contribute to a common fund to finance the activities. Activities: Studies and Reports (>120); International Research Networks : Wells, Risk, Monitoring, Modelling, Oxyfuel, Capture, Social Research, Solid Looping; Communications (GHGT conferences, IJGGC, etc); facilitating and focusing R&D and demonstration activities e.g. Weyburn 2

Members and Sponsors 3

3 rd Oxyfuel Combustion Conference Leon, Spain 9 th 13 th September 2013 Full Programme Announced 17 th May 2013 4

UPDATE TO THE CURRENT DEVELOPMENT OF OXYFUEL COMBUSTION 5

Alstom Schwarze Pumpe 2008 30MWth Lignite Hitachi Babcock Schwarze Pumpe 2010 30MWth Lignite IHI Callide 2011 30MWe Coal Alstom/ AL Lacq 2009 30MWth Gas/Oil? CIUDEN El Bierzo CFB Facility 2011 30MWth Coal CIUDEN El Bierzo PC Facility 2011 20MWth Coal 1980 s 1990-1995 EC Joule ThermieProject -IFRF / DoosanBabcock / Int l Combustion NEDO / IHI / JcoalProject ANL/Battelle/EERC completed the first industrial scale pilot plant Updated by S. Santos (20/08/12) 2003-2005 2007 Vattenfall(ENCAP ++) 1998 2001 CS Energy / IHI Callide Project CANMET US DOE Project / B&W / Air Liquide 2008 KEPCO/KOSEP - Yongdong(PC - 100MWe) FutureGen2 - Illinois (PC - 168MWe) Drax s White Rose Oxyfuel Project (300MWe) Endesa/CIUDEN -El Bierzo(CFB -300MWe) -??? 2009 Lacq World s first 30MWt retrofitted Oxy-NG boiler World s FIRST 30 MWt full chain demonstration at Schwarze Pumpe Pilot Plant B&W CEDF (30MWt) large scale burner testing started First large scale 35MWt Oxy-Coal Burner Retrofit Test done by International Combustion China: 3 Oxyfuel Projects in progress 2011 Callide World s first 30MWe retrofitted Oxy-coal power plant 2011 CIUDEN World s first 30MWt Oxy-CFB Pilot Plant By 2014-2018 Demonstration of 50 300MWe full scale power plant. Target : Commercialised by 2020 By the end of 2010/2011, Users (i.e. Power Plant Operators) will have 6 burner manufacturers fully demonstrating Utility Size Large Scale Burners which should give a high level of confidence toward demonstration B&W CEDF 2008 30MWth Coal Alstom Alstom CE 2010 15MWth Coal Doosan Babcock DBEL - MBTF 2009 40MWth Coal

Concluding Remarks Update to Key Demonstration Projects Based on the Conclusions from 2 nd Oxyfuel Combustion Conference This Technology is READY for DEMONSTRATION Lost of Janschwalde Project is a setback Success in the commissioning of Callide Project is an important milestone. Three important projects on-going FutureGen2 (USA) White Rose Project (UK) Yong Dong Project (South Korea) Other new projects currently under development Huazhong Project (China) 2 Other Oxyfuel Demonstration Projects under considersation in China 7

Presentation Outline Oxygen Production CO2 Processing Unit 8

Oxygen Production Facts: Today, only the Cryogenic Air Separation Unit or ASU is capable of delivering the oxygen demand of a large oxyfuel combustion boiler for power plant with CO2 capture For every 500MWe net output you will require ~10,000 t/d O2 o Low Purity (95-97%)* o Low Pressure (nearly atmospheric) At 95% purity will have 2% N2 and 3% Ar 9

Current Status and Challenges to Cryogenic ASU Advances and Development in ASU could result to 25-35% less energy consumption than what could be delivered by the current state of the art ASU today. A target of 140 kwh/t O2 is achievable These ASU would not be based on the conventional one but it could be hybrid based on 3 columns design or dual reboiler design. Challenges are: Cost of production of oxygen (energy consumption) ASU should address the needs of the requirements of power plant (i.e. Delivery, Flexibility, Turn-down, etc...) Utilisation of nitrogen within power plant or other users. Presented at Yokohama Workshop, March 2008 Presented at OCC2 - Yeppoon, Australia September 2011 10

Cryogenic Air Separation Capacity Increase 1902 : 5 kg/h (0,1 ton/day) 2006 : 1,250 Mio kg/h (30.000 ton/day) Linde AG Engineering Division 11 Bey/L/092009/Cottbus.ppt

Experience - Large ASU Projects and Train Scale-up Market drives ASU scale-up Proven 70% scale-up Quoting 5,000+ MTPD today 5000 4000 Rozenburg Oryx GTL Chevron Nigeria Eastman Texas A5000 / A7000 MTPD O2 3000 2000 Plaquemine Buggenum Polk 1000 0 1987 1993 1996 1996 2006 2009 2011 Startup date 12

Overview Of The Process Main and Boost Air Compression Air Cooling and Pretreatment Cryogenic Separation Storage Oxygen Air Heat Heat 14

Air Separation Process Conventional Design (mit Einblaseturbine) tauscher 5.5-6 bar 1.05 bar PGAN GOX Niederdruckkolonne Linde AG Engineering Division 15 Bey/L/092009/Cottbus.ppt Booster Turbine Wärmet 5.3-5.8 bar Hochdruckkolonne UKG Kondensator Oxygen: 95%, gaseous, at ambient pressure Features: PNitrogen: up to 30% of airflow available

ASU for Oxyfuel Combustion Applications There will be several ASU cycles for low purity oxygen requirements Leading ASU Cycle for Oxyfuel Combustion 3 Columns Dual Reboiler Key Features: Lower compression requirements for the air input to the cold box 16 16

McCabe Thiele Diagrams Equilibrium line Operating lines Double Column Single Pressure Side Column Reboiler Cold Compressed Side Column Reboiler 17

Case Studies Done by Air Products 18

ASU Cycle Comparison Results Without GAN, three column cycle is best 158 kwh/t(base) With GAN, three column cycle has lowest gross power - increasesdramatically for elevated pressure (EP) cycles as they make more GAN If GAN can be used (crediting avoided compression power) EP cycles are best EP: 128 kwh/t(-19%) 3 Col: 147 kwh/t(-7%) If GAN has no use and power is recovered with expander (no external heat), three column cycle is still best 157 kwh/t(-1%) 19

CAPEX vs OPEX (Source: NETL Report 2008) 20

ASU Interface to the Boiler An important aspects to this interface is the stability of the flame and you need to understand that flame stability envelope 21

For RETROFIT Case 22

ASU Addressing Flexibility Requirements Power plant requirements (i.e. regulatory framework) will define the design of the ASU choice between 2 trains vs multiple trains 23

ASU Addressing Flexibility Requirements Other options include the installation of liquid gas storage system could provide additional flexibility and opportunities 24

Key Concluding Remarks For the first and second generation Oxyfuel Combustion Technology, cryogenic ASU is the only way to deliver the oxygen demand of the boiler ASU interface to the boiler, operation issues such as flexibility, start up and shut down has been addressed. Delicate balance between CAPEX and OPEX REFERENCE ASU for Oxyfuel Combustion is now in place and ready to be demonstrated. Other emerging technologies such as ITM, OTM, etc are not ready in the near term. 25

Oxyfuel Coal Reference ASU Designs developed for a scalable reference plant Column diameters within manufacturing capabilities (referenced to 7000 te/d) Size te/d O 2 Machinery options Power MW 3,000 4,000 Centrifugal 1 or 2 train or axial 1 train 22-33 4,000 5,500 Centrifugal 1 or 2 train or axial 1 train 30-45 5,500 7,000 Centrifugal 2 train or axial 1 train 41-58 7,000-10,000 Centrifugal or axial 2 train 53-82 26

CO2 Processing Unit Key Areas of Development in CO2 Processing Unit or CPU o Compression and Removal of minor impurities (NOx, SOx and Other Trace elements o Dehydration Unit o Cryogenic Separation of Inerts (Cold Box development) o Additional capture of CO2 from the CPU Other key driver to the development is the specification of the CO2. o Management of CO2 purity requires good interaction between boiler, flue gas processing and CPU 27

Overview of Development of CPU over the last 8 years... Recognition of the NOx and SOx reaction by Air Products (presented during GHGT Conference June 2006) This has led to the rapid technology development among the industrial gas producers. Identification of potential impact of Hg to the operation of the CPU. Development of the use of impure CO2 as refrigerant driven mostly by reducing energy penalty. Work on further recovery of CO2 in the vent of CPU. 28

Air Products Oxy-Fuel CO 2 Capture and Purification with Air Products PRISM Membrane Boiler Steam Cycle Heat Recovery Needs Engineering Data Mature Tech, Needs Data Commercial Product CO 2 CO 2 Compression Raw Flue Gas Sour Compression & AP Acid Gas Column TSA Unit Mercury Removal Auto-Refrigerated N 2, Ar, O 2 Removal Process Condensate Collection Process Condensate Major Utilities Cooling Water Electric Power Offgas [To Atmosphere] O 2 and CO 2 Rich [To Boiler] Expander Optional APCI PRISM Membrane 29

Rectification Compressor building Analysis container Activated carbon filter Trailer docking station CO 2 -tanks (2x180 m³)

NOx SO 2 Reactions in the CO 2 Compression System We realised that SO 2, NOx and Hg can be removed in the CO 2 compression process, in the presence of water and oxygen. SO 2 is converted to Sulphuric Acid, NO 2 converted to Nitric Acid: NO + ½ O 2 = NO 2 (1) Slow 2 NO 2 = N 2 O 4 (2) Fast 2 NO 2 + H 2 O = HNO 2 + HNO 3 (3) Slow 3 HNO 2 = HNO 3 + 2 NO + H 2 O (4) Fast NO 2 + SO 2 = NO + SO 3 (5) Fast SO 3 + H 2 O = H 2 SO 4 (6) Fast Rate increases with Pressure to the 3 rd power only feasible at elevated pressure No Nitric Acid is formed until all the SO 2 is converted Pressure, reactor design and residence times, are important. 31

CO 2 Compression and Purification System Removal of SO 2, NOx and Hg 1.02 bar 30 C 67% CO 2 8% H 2 O 25% Inerts SOx NOx SO 2 removal: 100% NOx removal: 90-99% BFW Condensate 15 bar 30 bar cw Water 30 bar to Driers Saturated 30 C 76% CO 2 24% Inerts cw cw Dilute HNO 3 32 Dilute H 2 SO 4 HNO 3 Hg

The effect of Pressure on SO 2 and NO Conversion (1 sl/min, 7 and 14 barg) Presented at the 9th International Conference on Greenhouse Gas Control Technologies (GHGT-9) Purification of Oxyfuel-Derived CO 2, Vince White, Laura Torrente-Murciano, David Sturgeon, and David Chadwick, Washington, D.C., November 2009 Condensate Separator C MFC D From NRTF A Flue Gas Cooler B Reactor Compressor & Receiver Inlet 14 bar g After Compressor & Receiver Conversion Inlet 7 bar g After Compressor & Receiver Conversion (Point A) (Point C) (Point A) (Point C) ppm SO2 900 20 98% 950 150 84% ppm NOx 520 50 90% 390 120 68% 33

DOE/NETL Cooperative Agreement: Air Products Sour Compression PDU Side View of PDU Acid Reactor (C102) 1 st campaign Jan 2010 2 nd campaign April-May 2010 34 U.S. Department of Energy's National Energy Technology Laboratory under Award Number DE-NT0005309

LICONOX Process Linde AG Engineering Division 36 Bey/L/092009/Cottbus.ppt

Sulphuric Acid Method Activated Carbon Method

Auto-Refrigerated Inerts Removal Removal of impurities minimises compression and transportation costs. O 2 can be removed for EOR-grade CO 2 CO 2 capture rate of 90% with CO 2 purity >95% CO 2 capture rate depends on raw CO 2 purity which depends on air ingress Increases from zero at 25mol% to 90% at 75mol% Reducing air ingress increases CO 2 capture rate 41

Can we improve on ~90% CO 2 Capture? Vent stream is at pressure and is CO 2 (and O 2 ) rich Flue Gas Vent 1.1 bar ~25% CO 2 ~25% O 2 ~50% N 2 Flue Gas Expander Flue Gas Heater Aluminium plate/fin exchanger -55 C Driers 42 30 bar Raw CO 2 Saturated 30 C 75-85% CO 2 CO 2 product ~96% CO 2 ~4% Inerts -60 C dp

25%mol CO2 75% inerts (~ 15% O2) 25%mol CO2 75% inerts (~ 19% O2) 76%mol CO2 24% inerts (~ 5-6% O2) 96%mol CO2 4% inerts (~ 0.95% O2) 72%mol CO2 28% inerts (~ 5-6% O2) 98%mol CO2 2% inerts (~ 0.6% O2) 25%mol CO2 75% inerts (~ 15% O2) 25%mol CO2 75% inerts (~ 15% O2) 72%mol CO2 28% inerts (~ 5-6% O2) 99.95%mol CO2 0.05% inerts (~.01% O2) 72%mol CO2 28% inerts (~ 5-6% O2) 99.999%mol CO2 0.001% inerts (~.0005% O2) 43

Autorefrigeration Process J-T expansion of purified LCO 2 for refrigeration Raw CO 2 partially liquefied by boiling product Compared to NH 3 refrigeration: Simpler process Lower CAPEX Vent Dryer Hg > 99.9% CO 2 PHX Higher CO 2 recovery Lower power Distillation Column Reboiler Cold Box US Pat. 7,666,251 44

Air Products Oxy-Fuel CO 2 Capture and Purification with Air Products PRISM Membrane Flue Gas Expander Flue Gas Heater To Boiler Membrane Aluminium plate/fin exchanger -55 C Driers 45 30 bar Raw CO 2 Saturated 30 C 75-85% CO 2 CO 2 product ~96% CO 2 ~4% Inerts -60 C dp

VPSA (Vacuum Pressure Swing Adsorption) for Recovering CO 2 from Cold Box Vent CO 2 rich recycle VPSA CO 2 lean vent 100% 90% Cold box + VPSA Cold box Vent Feed CO 2 CO2 Recov very, % 80% 70% 60% 50% Cold box 40% 0% 3% 6% 9% 12% Air Ingress, % Cold Box 49

Some More Challenges... Demand of the quality requirements of the CO2 from the power plant for transport and storage. What are the Required Specification? Further recovery of CO2 from the vent will make oxyfuel more competitive if high recovery of CO2 is required! Need a large scale demonstration of the CO2 processing unit using impure CO2 as refrigerant. 50

51 5

Email: Website: Thank you stanley.santos@ieaghg.org http://www.ieaghg.org 53