Development of Membrane Technology for CO …

1 Development of Membrane Technology for CO2 Capture at MTRTim MerkelMTR Director of R&DSeptember 28, 2012 Symposium for Innovative CO2 Membrane Separation TechnologyTokyo, JapanPersonal Connection to Japan2 Koizumi Yakumo (Lafcadio Hearn) Lives in Japan 1890-1904 Teaches in Matsue and Tokyo University Translates Japanese stories to English (Kwaidan) Was Tim s great, great, great uncleIntroduction to MTR3 Japan~8,000 kmNatural Gas:Petrochemicals:Hydrogen (Refinery):H2/CH4, CO, CO2 Propylene/NitrogenCO2/CH4, CH4/N2 NGL/CH4 MTR designs, manufactures, and sells Membrane systems for industrial gas separationsCustomers include:BP, Chevron, Dominion Exploration, Ercros, ExxonMobil, Formosa Plastics, Innovene, Sabic, Sasol, Sinopec, Solvay, and to MTR4 The Climate is Changing5 Muir Glacier, Alaska 63 years laterFossil Fuel Use And Atmospheric CO2 Concentration Are IncreasingSlide courtesy of Dr.

2 S. Julio Friedmann, Lawrence Livermore National Laboratory6 How To Cut Emissions: The Wedge Approach Use multiple CO2reduction strategies including CO2capture from large sources 8 wedges needed to maintain CO2at 500 ppm (each wedge 4 billion tons/y CO2) Japan is world leader in CO2emission reductions (Kyoto Protocol 1997)Source: Pacala and Socolow, Science, 20047 Wedges include: Improved energy efficiency Alternative energy (wind, solar) Nuclear power Efficient biofuels Conservation of natural sinks Carbon capture and sequestration Rules of thumb: Coal power Oil transportation Natural Gas mixed 5,000 coal-fired power plants worldwide Fossil fuel share of electricity generation (IEA WEO 2010): 2008 75% 2035 71%Source: International Energy Agency (IEA) (2008), CO2 Emissions from Fuel Combustion, 2008 CO2 Emissions by Sector Power Plants Generate >40% of CO2 Emissionsced All options involve separations where membranes could play a role To use membranes effectively, important to understand the process CO2 Capture Options for Fossil Fuel Power Membrane advantages: simple passive operation, small footprint, no water or hazardous chemicals used, energy efficient - no steam used Hot syngas cleanup membranes offer potential for process intensificationGasifierCoalCO2O2 SyngasQuenchWGSreactorsSteamSteamASUAirS yngas cooling2-stageSelexolCO2compCombustiontu rbineSyngas reheatH2 Polymer membranes; CO2or H2-selectiveMembrane reactors.

3 Metal and ceramic membranesH2-selectiveDirty, hotsyngasRelatively clean, cool syngas40 C210 C270 C35 C195 C600 C50 bar30 bar55 bar150 barCO2storageIncreasingly harsh operating conditions Pre-Combustion CO2 Capture MembranesAirN2 Can operate warm/hot to reduce the need for heat exchange Can use nitrogen sweep to maintain permeate fuel gas at turbine pressure Water goes with fuel gas; reduces CO2dehydration costsH2-Selective Membranes Offer AdvantagesGasifierCoalCO2O2 SyngasQuenchWGSreactorsSteamH2membraneSt eamASUAirCO2compCombustionturbine600 C210 C150-250 C50 bar55 bar150 barCO2storageN2 diluentH2 + N2 AirH2-selective Membrane , ,000 Upper boundaH2 permeance (gpu)Pu re-gasH2/CO2selectivityMTR Proteus(mixed gas at 150 C)PBIb (250oC)Crosslinked modifiedpolyimidescPBI-basedd(mixed gas at 250oC)Need Membranes With Good H2/CO2 Selectivitya) Robeson et al., JMS 320,390-400 (2008); assumes a 1 m selective ) O Brien K.

4 Et al., DOE NETL project fact sheet 2009; assumes a 1 m selective ) Low, , et al., Macromolecules 41(4), 1297-1309 (2008); assumes a 1 m selective ) Krishnan, G., 2010 NETL CO2 Capture Technology Conference, Pittsburgh, PA and Klaehn, J., et al.,NAMS 2011, Las Vegas, adapted from: B. W. Rowe et al., JMS 360, 58 69 (2010).High Temperature Improves Performance1101001,000204060801001201401 60180 Pure-gas permeance (gpu)Temperature ( C)H2CO2 MTR ProteusTMPermeanceTrade-off ,000H2/CO2 selectivityH2 permeance (gpu)200 K250 K300 K350 K400 K297 K383 KProteusTMAssumes a selective layer thickness of micronField Tests with Coal-Derived Syngas The National Carbon Capture Center (NCCC) in Wilsonville, Al allows slipstream testing of pre-combustion and post-combustion capture technologies1101001,0000510152025 Mixed-gas permeance (gpu)Time (days)CO2H2135 C120 C120 C135 C05101520253035400510152025 Time (days)Mixed-gas H2/CO2 selectivity120 C135 CPermeanceSelectivity Tests were conducted at the National Carbon Capture Center (NCCC)

5 Run by Southern Company The coal-derived syngas feed contained 780 ppm H2S Field Tests Show Stable PerformanceProcess Economic Analysis With DOE/NETL16 Collaborated with DOE NETL and WorleyParsons to analyze MTR process Comparison made with Case 2 of DOE Bituminous Baseline report (GEE Gasifier with 2-stage Selexol) Several sulfur handling options considered (co-sequestration, warm gas cleanup, etc); post Membrane MDEA selected as low cost Membrane process uses 5% less energy and gives a 7% lower cost of electricity compared to Selexol Higher Membrane H2/CO2selectivity would help (particularly up to 40, beyond which diminishing returns) H2-selective membranes have greater potential than CO2-selective membranes for oxy-blown gasifiers because: They can be operated hot (>100 C) so that syngas cooling/water KO equipment and syngas reheat/humidification can be reduced or avoided They can be swept with N2available from the ASU to reduce energy requirements They send water to the fuel gas, reducing CO2dehydration costs Polymer membranes are low cost and sulfur tolerant a huge advantage Membranes are already competitive with absorption, but better selectivity would lower energy use and cost Not much data on polymer membranes above 100 C significant potential to uncover better materialsPre-Combustion Summary Generating affordable pressure ratio is the key challenge for membranes Limited use for high selectivity because of pressure ratio limitations Volumetric flow is enormous.

6 Membranes must have high CO2permeance Single-stage Membrane process will not give high purity and recoveryPost-Combustion CO2 Capture with MembranesBoilerCoalCO2 AirESPFGDAshSteam to turbinesSulfur 600 MWe 500 Nm3/s = 1,540 MMscfd flue gas 10 15% CO2in N2= 10,000 ton CO2/day at low pressure Combustion air sweep provides driving force w/o compression or vacuum Pre-concentrated CO2decreases Membrane area and power required The MTR CO2 Capture Process1918 % O2, 8 % CO220% CO2CO2 depletedflue Patents 7,964,020 and 8,025,715 Promising Membrane Development1101001,0001101001,00010,0001 00,000 Upper bound (2008)a CO2 permeance (gpu)Pure-gasCO2/N2selectivityMTR (2008)cGKSS (2010)eUT Austin (2006)bU. Twente(2010)da) Robeson et al., JMS 320, 390-400 (2008); assumes a 1 m selective ) Lin et al., JMS 276, 145-161 (2006); assumes a 1 m selective ) Merkel et al.

7 , ICOM 2008, Honolulu, ) Reijerkerk et al., JMS 352, 126-135 (2010); assumes a 1 m selective ) Yave et al., Nanotechnology 21, 395301 (2010); and Yave et al., Macromolecules 43, 326-333 (2010).RITE, NTNU21 High CO2 Permeance Most Importantto Reduce CostLimited affordable pressure ratio reduces the benefit of high cost ($/ton CO2) Membrane CO2/N2 selectivity2,000 gpu1,000 gpu4,000 gpu90% CO2 capturePressure ratio = 1CO2 permeancePolarisTM 3221 TPD Test System at NCCC1 TPD system installed Oct/Nov 2011; continuous operation spring 2012 Module NumberNormalized CO2 PermeanceAfter TestNormalized CO2/N2 SelectivityAfter Test5839(Cross-flow)110%118%5879(Sweep)1 08%96%Fresh moduleAfter 45 days operation at ChollaTest Results: Modules Are Stable1 TPD NCCC Results: Stream Compositions24 As expected, Membrane enriches CO2by about 6 times in the permeate Initial low feed CO2content due to air ingress Most variation in compositions due to daily temperature swings Overall, Membrane module performance is stable11010005001,0001,500CO2 content (%)Operating time (hours)Flue gas outageAnalyzermalfunctionCO2-enrichedper meateFeedCO2-depletedresidue1 TPD NCCC Results.

8 CO2 Capture Rate Initially system operating at ~2/3 capacity After 1,000 hours, additional modules loaded to increase capture rate to 85%25020406080100050010001500CO2 capture rate(%)Operating time (hours)Flue gas outageAnalyzermalfunctionNext Steps: 20 TPD System26 Estimate installation at NCCC in 2ndquarter 2013 Operate system at NCCC for 6+ months; at least 3 months of continuous SS operation System demonstrates large bundled spiral-wound modules20 TPD System at NCCC1 MWFlue Gas InFlue Gas MWepilot solventtest unitPicture courtesy of Mr. Tony Wu, Southern Company27 Future Scale-UpOne module skid, 2500 m2 Smaller foot print Low pressure drop Reduced manifolding Lower cost40 modules plant, 100 MWe62 ft44 ft64 ft27 ft28 Sweep operation: Increases the CO2in the flue gas from 4% to 20% for gas turbines Reduces the quantity of flue gas going into the CO2capture unit by a factor of 3 Hybrid design with absorption avoids the use of compression/vacuum equipmentOther Concepts: Sweep-Assisted Hybrids Energy and cost constraints limit the practical pressure ratio available.

9 High permeance, modest selectivity membranes are preferred A large research effort is producing better membranes Selective recycle is a useful way to pre-concentrate CO2 Membranes can play a role in post-combustion capture, probably in a hybrid system (cryogenic, amine, etc) Membrane testing is at the small slipstream stage Post-Combustion Membrane SummaryAcknowledgements MTR Xiaotong Wei, Zhenjie He, Karl Amo, Steve White, Haiqing Lin, Meijuan Zhou, Sylvie Thomas, Richard Baker, Hans Wijmans, Saurabh Pande Department of Energy,National Energy Technology Laboratory Rick Dunst and Jose Figueroa Southern Company Tony Wu, Frank Morton, and John WheeldonAcknowledgementsEffect of Membrane Properties on COE All calculations for 90% CO2 capture Design uses minimal feed compression (booster fan only) Higher permeance (lower cost) membranes are key to approaching DOE goals33304050607080900 COE(%)Permeance-normalized Membrane cost ($/m2 gpu)1st Generation Polaris2nd Generation PolarisMEA (DOE Case 10)DOE TargetAdvancedPolarisMTR MembraneProcess( Bar Feed)Higher permeance membranes