ITM Technology for Carbon Capture on Natural Gas

ITM Technology for Carbon Capture on Natural Gas and Hybrid Power Systems John Repasky, David Mc. Carthy, Phillip Armstrong, Michael Carolan Workshop on Technology Pathways Forward for Carbon Capture & Storage on Natural Gas Power Systems 1 Organized by U. S. Energy Association Supported by U. S. Dept. of Energy Washington, DC, USA April 22, 2014 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Who is Air Products? l Merchant Gases – Industrial, medical, and specialty gases supplied to wide array of applications l Tonnage Gases, Equipment and Energy – Industrial gases supplied via large on-site facilities or pipeline systems; equipment; technologies to serve future industrial and energy markets l Electronics and Performance Materials – Specialty and tonnage gases/chemicals, services and equipment supplied to electronics markets; performance chemical solutions for a variety of industries FORTUNE 500 COMPANY ♦ $10. 2 BILLION SALES FY 13 ♦ SAFETY LEADER 21, 600 Employees ♦ Operations over 50 countries ♦ Sales over 100 countries Production Operator, Equipment & Plant Sales, Pipelines & Distribution 2 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Air Products & CO 2 Capture for EOR Port Arthur, Texas · Solutions for the EOR Industry - Developing, financing, constructing, and operating CO 2 processing facilities - Helium Recovery Project - Port Arthur CO 2 Project - New H 2 S Removal Technology, NGL recovery Industrial CO 2 Europe, Americas · Industrial CO 2 business in Americas & Europe - Recent purchase of EPCO CO 2 business · CO 2 Capture R&D - Evaluation and development of broad range of CO 2 Capture Technologies - Pilot demonstration of CO 2 processing unit for oxyfuel combustion of coal at Vattenfall’s research and development facility in Schwarze Pumpe, Germany 3 CO 2 Capture Pilot Germany © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Air Products Port Arthur CO 2 Project is approaching 1 million tonnes CO 2 · 90%+ CO 2 capture from 2 steam-methane reformers (Vacuum Swing Adsorption) · ~30 MWe cogeneration unit to generate power and makeup steam · ~925, 000 tonnes CO 2/year Denbury “Green” pipeline for EOR in Texas at West Hastings oil field · Total Project: $431 Million DOE Share: $284 Million (66%) Source: Air Products and NETL CO 2 Capture On-stream: PA-II SMR – December 2012 PA-I SMR – March 2013 Full capacity achieved April 2013 4 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Technology targets low cost oxygen: enables pre-combustion & oxyfuel CO 2 capture Post-combustion capture Pre-combustion capture O 2/CO 2 recycle (oxyfuel) combustion capture 5 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Air Products’ ITM Technology • Ion Transport Membranes (ITM) provide oxygen at high-purity and high-flux - Non-porous mixed conducting ceramic membranes Operate at high temperature, in the range 700 to 1000 C • Started R&D in 1988 • Currently 90 U. S. Patents and global equivalents - Materials and catalysts Membrane and module structures Process cycles Applications and integrations • U. S. DOE Cooperative Program since 1998 Ion Transport Membranes are a Platform Technology • ITM Oxygen – Tonnage Oxygen Supply • ITM Syngas – Tonnage Syngas/Hydrogen Supply 6 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

What is ITM Oxygen ? A proprietary ceramic membrane to separate oxygen from air – Inputs are high pressure air and heat/fuel – Outputs are oxygen and power/steam Pressurized Air Heat/Fuel Oxygen ITM Oxygen Power/Steam Unique technology gives high oxygen flux, high selectivity, and integrates well with high -temperature energy applications 7 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen integrates well with power generation cycles STEAM OXYGEN HRSG AIR ELECTRIC POWER OXYGEN BLOWER FUEL ‘AIR’ OXYGEN HEAT EXCHANGE 8 ION TRANSPORT MEMBRANE © Air Products and Chemicals, Inc. 2014. All Rights Reserved

How does ITM technology reduce the cost of oxygen for carbon capture? Post-combustion capture Pre-combustion capture O 2/CO 2 recycle (oxyfuel) combustion capture 9 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen integrates oxygen production and power/steam generation CO 2 Coal, NG Syngas Gen. syngas CO 2 Removal H 2 -rich fuel CC Power Gen. Power ITM Oxygen IGCC/H 2 -fired GT Pre-combustion capture 10 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen integrates oxygen production and power/steam generation CO 2 -rich flue gas Oxy-Comb. Coal, (e. g. Boiler) NG CO 2 Purif. CO 2 Power Oxygen NG CC Power Gen. ITM Oxygen Power NGCC + Oxy-Coal Hybrid O 2/CO 2 recycle (oxyfuel) combustion capture 11 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

The Electric Power Research Institute (EPRI) with Air Products and Worley Parsons conducted power plant assessments: IGCC & Oxy-combustion with carbon capture l l Compared ITM Oxygen with traditional air separation units (ASU) integrated into power plants Greenfield design basis included discussions with boiler and turbine manufacturers IGCC 765 MWgross IGCC F-class GT CO 2 capture percentage 87% Oxy-combustion 800 MWgross SC PC boiler 90% ITM advantage relative to cryo ASU case Efficiency advantage 1. 8 %pt 2. 5 %pt Unit capital cost advantage 12 % 18 % LCOE* advantage 10 % 5% * Levelized Cost of Electricity 12 Reference publication: AICh. E Spring Mtg, April/May 2013. 75% 7. 6 %pts 34 % 20 % © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion Broad, multi-disciplinary team 13 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion Over 1000 days of operation have demonstrated oxygen purity, oxygen flux, and pressure/temperature cycling. Commercial modules and next generation components continue to be tested. Recently relocated from Sparrows Point, MD to Convent, LA U. S. A. 14 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion Intermediate-Scale Test Unit is in start-up for operation in 2014. “ISTU” Convent, LA U. S. A. 15 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion ITM Vessel Intermediate-Scale Test Unit is in start-up for operation in 2014. “ISTU” Convent, LA U. S. A. 16 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion Ceramic Fabrication scale-up is in commissioning to support Next Phase Energy Scale Development. “Cer. Fab” Tooele, UT U. S. A. 17 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Oxygen: DOE Cooperative Program • Phase 1: Technical Feasibility (0. 1 TPD O 2) • Phase 2: Prototype Testing (1 - 5 TPD O 2) Current activity Phases 3 and 5 are being conducted simultaneously • Phase 3: Intermediate Scale Testing (100 TPD O 2) – 12 MW IGCC • Phase 4: Reaction Driven Membranes • Phase 5: Ceramic Module Fabrication to Supply 2000 TPD O 2 Facility • Planning Next Phase: Energy Scale Development (2000 TPD O 2) - equivalent 250 MW IGCC or 110 MW oxycombustion ISTU and Cer. Fab are critical steps to commercialize energy-scale ITM Oxygen. Actively pursuing early commercial opportunities. 18 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Syngas is a revolutionary technology, which integrates oxygen production & syngas generation in a single unit CO 2 NG ITM Syngas syngas CO 2 Removal H 2 -rich fuel CC Power Gen. Power NGCC/H 2 -fired GT Pre-combustion capture 20 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Air Products evaluated ITM Syngas to co -produce H 2 and CO 2 toward decarbonized fuel application 21 l Compared ITM Syngas with conventional processes based on ATR/ASU to produce 150 to 760 MMscfd fuel-grade H 2. l ITM Syngas showed potential for 30% capital cost savings in the synthesis gas generation process area and over 20% capital cost savings for the overall synthesis gas/H 2/CO 2 production process. l ITM Syngas showed thermal efficiency advantage of 3 percentage points. Reference publication: AICh. E Spring Mtg, April 2005. © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Syngas Development Program • Phase 1: Laboratory-scale Materials and Membrane Development • Phase 2: Two-levels of Scale-Up • 27 Nm 3/h, 24, 000 scfd Process Development Unit (PDU) Current activity is focused on scale-up • 280 Nm 3/h, 0. 25 million scfd Subscale Engineering Prototype (SEP) • Phase 3: Early, Small, Commercial-Scale Unit Broad, multi-disciplinary team 22 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Syngas Development Program • Phase 1: Laboratory-scale Materials and Membrane Development • Phase 2: Two-levels of Scale-Up • 27 Nm 3/h, 24, 000 scfd Process Development Unit (PDU) Current activity is focused on scale-up • 280 Nm 3/h, 0. 25 million scfd Subscale Engineering Prototype (SEP) • Phase 3: Early, Small, Commercial-Scale Unit Commercial-size membranes have been operated through a wide range of conditions for over 150 days. Allentown, PA U. S. A. 23 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Syngas Development Program • Phase 1: Laboratory-scale Materials and Membrane Development • Phase 2: Two-levels of Scale-Up • 27 Nm 3/h, 24, 000 scfd Process Development Unit (PDU) Current activity is focused on scale-up • 280 Nm 3/h, 0. 25 million scfd Subscale Engineering Prototype (SEP) • Phase 3: Early, Small, Commercial-Scale Unit 27 280 • Engineering Prototype will position ITM Syngas ready for 24 • early commercial operation Support sought for scale-up to the Engineering Prototype © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Technology is Attractive across Broad Range of Applications ITM Oxygen ITM Syngas • Clean energy • Hydrogen production • Gasification: IGCC, Polygen, Ct. L, Xt. L, decarbonized fuel • Syngas for GTL • Oxy-combustion • Centralized de-carbonized fuel for distributed H 2 fuel • Traditional energy-intensive industrial production • Enables high degree of CO 2 capture 25 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

ITM Technology shows significant benefit in both capital cost and energy savings across broad range of oxygen-based applications, including power generation with CCS • ITM Oxygen integrates oxygen production and power generation • ITM Syngas is a revolutionary technology that combines oxygen production and syngas generation in a single unit operation • ITM Technology is well positioned to meet the needs of clean energy applications - We are actively pursuing early commercial opportunities - Additional development supporters are welcome 26 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Acknowledgement This technology development has been supported in part by the U. S. Department of Energy under Contract No. DE-FC 26 -97 FT 96052 and Contract No. DE-FC 26 -98 FT 40343. The U. S. Government reserves for itself and others acting on its behalf a royalty-free, nonexclusive, irrevocable, worldwide license for Governmental purposes to publish, distribute, translate, duplicate, exhibit and perform this copyrighted paper. Disclaimer Neither Air Products and Chemicals, Inc. nor any of its contractors or subcontractors nor the United States Department of Energy, nor any person acting on behalf of either: 1. Makes any warranty or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or 2. Assumes any liabilities with respect to the use of, or for damages resulting from the use of, any information, apparatus, method, or process disclosed in this report. Reference herein to any specific commercial products, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Department of Energy. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Department of Energy. 27 © Air Products and Chemicals, Inc. 2014. All Rights Reserved

Thank you… tell me more ITM Oxygen - “Ceramic and Coal: ITM Oxygen for Power Generation with Reduced CO 2 -Emissions, Detailed Engineering Study Results”, Air Products/ EPRI/Worley. Parsons, AICh. E Spring Mtg, San Antonio, TX, April/May 2013. (Oxycombustion & IGCC Economics) - “ITM Oxygen Technology: Scale-up Toward Clean Energy Applications”, Intl Pittsburgh Coal Conf. , Pittsburgh, PA, Oct 2012. (Program Update) www. airproducts. com ITM Syngas - “Advances in ITM Technology for Syngas Production”, Air Products/ Ceramatec, 10 th Natural Gas Conversion Symposium (NGCS Doha 2013), Doha, Qatar, March 2013. (Program Update) - “ITM Syngas: Ceramic Membrane Technology for Lower Cost Conversion of Natural Gas”, Air Products/Chevron/Sasol, AICh. E Spring Mtg, San Antonio, TX, March 2010. (Program Update & Economics) 28 ITM@airproducts. com Phone: +1 610 481 4475 Fax: +1 610 706 7420 © Air Products and Chemicals, Inc. 2014. All Rights Reserved