Advances in amine scrubbing since Bellingham Research ...
THE UNIVERSITY F TEXAS AT AUSTIN T H E U N IOV ERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Texas Carbon Management Program Research needs and opportunities for amine scrubbing for gas combustion Gary T. Rochelle Department of Chemical Engineering WORKSHOP ON TECHNOLOGY PATHWAYS FORWARD FOR CCS ON NATURAL GAS POWER SYSTEMS Washington, DC 20004 April 22, 2014 THE UNIVERSITY OF TEXAS
AT AUSTIN Texas Carbon Management Program Messages Bellingham demonstrated technical feasibility Advanced processes improve economics, but need D & Demo Better solvents Better processes Bigger & Better equipment Environmental issues need preemptive resolution Oxidation, Nitrosation, Amine reclaiming, Amine Better Second Generation Solvents Properties at natural gas conditions, PCO2*= 0.1/1 kPa kgavg x1e7 CC -CHABS Tmax Solvent (mol/ (m) (mol/kg) (kJ/mol) (C) 2 sPam ) 7 MEA 12
Scrubbed Flue Gas to Atmosphere DCC not needed for for Advanced Absorber water NGCC Less Packing, Richer Lean Amine Solvent No Prescubbing or DCC RECYCLE INTERCOOLING to Cool Gas Wet/Dry ?? HOT Flue Gas In RECYCLE INTERCOOLING TO Replace DCC Rich Amine Advanced flash stripper reduces Weq 8 m PZ at 0.25 lean loading 6 bar/150oC reduces compressor cost CO2
Wpump= 4.4 kWh/tonne Wcomp= 67.6 Wreb= 155.3 WEQ= 227.3 20K LMTD Cold Rich BPS 9% 6.2 bar Warm Rich BPS 30% 127 oC (BP) Qreb=2.3 GJ/tonne Rich Solvent 0.36 Ldg Lean Solvent 0.25 Ldg Flash Avg DT=5 K 150 oC 5 W E Q (k W h / to n n e C O Gas takes 10% more energy than coal
0.30 0.32 Lean loading (mol CO2 / mol alkalinity) 0.34 6 THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Bigger and better Equipment needs D & D Absorber - Single Vessel for 250 MW gas = 19 m Square, concrete, low DP packing Stripper - 7.5 m for 2 bar, 5 m for 8 bar Reboiler/convective steam heater
Multiple, larger plate and frame exchangers Materials Selection/Corrosion CS, SS, Concrete, polymer? Effective heat integration with NGCC 7 THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Oxidation Amine Oxidation will be more significant with gas than with coal O2/CO2 = 5 for gas vs 0.4 for coal MEA makeup at Bellingham = 3 lbs/ton CO 2 Economically acceptable C= 2-3 $/ton CO2 Environmentally questionable : NH3, aldehydes, et al. Advances in Understanding, gained mostly with air/CO 2:
catalysts/inhibitors; O2 mass transfer, thermal cycling Identified mitigation options need to developed and demonstrated N2 stripping, Inhibitors, Solvent Selection 8 THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Nitrosation Secondary amines react quantitatively with NO 2 to make carcinogenic nitrosamines, R2N-N=O Nitrosation will be more significant with gas NOx/CO2 = 10 ppm/3% > 10 ppm/12% Because of degradation all solvents will nitrosate Identified mitigation options need development & demonstration
Thermal decomposition at 150oC Prescrubbing to remove NO2 Reclaiming to concentrate and remove Water Wash to avoid gas emissions 9 THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Solvent Reclaiming Required for degradation products, RNNO, sulfate, nitrate, metals Effective reclaiming eliminates need for gas prescrubbing Thermal reclaiming of nonvolatile impurities
Bellingham demonstrated1G thermal reclaiming w gas impurities 2G thermal reclaiming will reduce amine losses Less attractive alternatives required for nonvolatile solvents Ion exchange, Electrodialysis, Precipitation Volatiles processing to remove NH3, aldehydes, et al. All need development & demonstration with long term operation 10 THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program Amine Aerosols / Water Wash Amine aerosol growth degrades water wash performance Amine aerosols will be less significant with gas No SO3 or fly ash However ambient particulate & SO2 may be
problematic Needs science and monitoring on variable gas sources 11 THE international meeting on CCS Austin Convention Center Hosted by UT with IEAGHG Rochelle co-chair of Steering 1500+ participants Sponsorship opportunities: contribute $10k, 25k, or 50k Exhibitor: $5k www.GHGT.info October 5 - 9, 2014 | AUSTIN, TX - USA PCO2, OUT 0.3 kPa PCO2, OUT 1.2 kPa NATURAL GAS TURBINE vs. COAL BOILER (8m PZ) P*CO 0.1
CO2 to Compression 2, LEAN kPa P*CO2, LEAN 0.4 kPa Absorber Stripper Main Cross Exchanger Reboiler Flue Gas In PCO2, IN 3 kPaP*CO2, RICH 1 PCO2, IN 12 kPa Opportunities: Natural Gas Turbine vs. Coal Boiler Benefits of leaner loading range 1) Higher CO2 absorption rate constant DCO2 k 2 Am Increased free amine N CO2 LMPD ~2x coal reaction rate
H CO2 2) Improved Operating Solvent Capacity Flat VLE curve in NG loading range ~20% increase in CO2 capacity per kg solvent circulated Recycle intercooling to cool gas Cool gas in absorber to reduce overall column temperatures 14 Challenges: Natural Gas Turbine vs. Coal Boiler Lower flue gas CO2 concentration => Smaller driving force Coal: ~3.2 kPa LMPD; NG: ~0.8 kPa LMPD Lower CO2 pressure in stripper (leaner loading range => reduced PCO2) More mechanical compression More H2O vapor per mole of CO2 (irreversible losses in condensation) 15 Larger gas volume Column diameter increases
Blower size increases Bellingham, NGCC, 1991-2005 98.5% on stream in 2004 40 MW Slipstrm 13 % O2 3 % CO2 7? % H2O o 150? C 16 Air Cooled Reddy et al., 2003 Chapel et al., 1999 Sander & Mariz, 1992 14 tonne/hr 1.5-2 bar 1101200C
3 lbs MEA/t CO2 4.2 GJ/t (?) 30-50 psig Kettle makeup (?) Bellingham, NGCC, Fluor Stripp er 3x40 m 17 Sander and Mariz, 1992 Absorb er 7.5x55 m DCC 8.4x21m Case Studies Combined cycle gas turbine 3 4.5% CO2; 6 8% H2O
8m PZ solvent LLDG = 0.25 mols CO2/mols alkalinity NEW ABSORBER CONCEPTS Recycle Intercooling Removing Direct Contact Cooler 18 Scrubbed Flue Gas to Atmosphere No Intercooling Lean Amine Gas In Flue Gas IN DCC Rich Amine L/G (mol/mol) 5.0 0.279
Removing the Direct Contact Cooler 24 Scrubbed Flue Gas to Atmosphere BASE CASE WITH DCC RECYCLE INTERCOOLING Gas In Flue Gas IN DCC Rich Amine 90% Removal Lean = 0.250 mols CO2/mols alkalinity 65 Rich = 0. 358 mols CO 2/mols alkalinity Interfacial Area (1000 m2) : 289 L/G = (1.2*Lmin) = 1.106 mol/mol 60 TLiquid in : 40C TFlue gas in : 40C
5E-06 WITH DCC 4E-06 Molar Flux (kmol CO2/s/m2) Temperature (C) 70 3E-06 55 50 Molar Flux CO2 MAX T = 47.1 C 2E-06 Liquid T 45 1E-06 Vapor T 40
Bottom Scrubbed Flue Gas to Atmosphere NEW DESIGN NO DCC Lean Amine RECYCLE INTERCOOLING RECYCLE TO REPLACE DCC HOT Flue Gas In Rich Amine 90% Removal Lean = 0.250 mols CO 2/mols alkalinity 65 Rich = 0.355 mols CO /mols alkalinity 2 2 Interfacial Area (1000 m ): 286 L/G = (1.2*Lmin) = 1.134 mol/mol 60 TLiquid in : 40C TFlue gas in : 121C 5E-06
NO DCC 4E-06 Molar Flux (kmol CO2/s/m2) Temperature (C) 70 3E-06 Vapor T 55 Molar Flux CO2 MAX T = 47.7 C 50 2E-06 45 Liquid T 1E-06 40 35
28 TGAS, MIN = 41.2 C 0 Top 0.1 0.2 0.3 0.4 0.5 0.6 Z/ZTOTAL 0.7 0.8 0.9 1 0E+00
Bottom THE UNIVERSITY OF TEXAS AT AUSTIN Texas Carbon Management Program No DCC vs. DCC Nearly identical absorber packing requirement & rich loading Performance & profiles without DCC replicate DCC case Trade-off: Additional intercooling loop vs. cost of DCC Operational risk: reliability of wet-dry interface Simple Stripper using 8 m PZ 6 bar/150oC reduces compressor cost Condenser CO2 150 bar
6~12 bar Compressor Cross exchanger CO2 Rich Solvent ~140 oC Stripper 1 bar 150 oC Pump Trim cooler CO2 Lean Solvent Reboiler 30 R e b o i le r d u t y ( G J / t o n n e C O 2 ) Reboiler duty (GJ/tonne CO2) 3.0 Simple Stripper (NG, Rldg=0.36)
0.32 0.34 31 UNIVERSITY W (k W h /to n n e C O 2 THE OF TEXAS AT AUSTIN Energy Analysis Texas Carbon Management Program Estimated Total Equivalent Work 12% CO2, 90% Removal, 150 bar, 40 C Wequiv 0.75Q Tstm Tsink Wcomp Wpump Tstm
500 400 MEA Minimum Work = 109 kWh/tonne = 0.39 GJ/t 300 1.08 GJ/t PZ 0.72 GJ/t CO2 Separation = 46 kWh/tonne = 0.17 GJ/t 100 Compression = 63 kWh/tonne = 0.23 GJ/t 200 0 2000 2004 2008 Year 32
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