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RTI International
RTI International is a trade name of Research Triangle Institute. www.rti.org
RTI’s Carbon Capture Experience Luke Coleman, PhD
Program Manager – Carbon Capture Energy Technology Division
RTI International
June 2, 2014
Copyright © 2014 RTI. All rights reserved
RTI International
One of the world’s leading research organizations
• RTI is an independent, nonprofit institute that provides research, development and technical services to government and commercial clients worldwide
• Our mission is to improve the human condition by turning knowledge into practice
• Located in Research Triangle Park, NC
RTI International Turning Knowledge Into Practice
RTI International Technology Development with RTI
RTI develops advanced process technologies in partnership with leaders in energy
Span the gap between University R&D and Industry Deployment
Full alignment with industry objectives – Defined commercialization pathways – Flexible intellectual property arrangements – Potential leveraging of industrial R&D
funding with government provided funding
Biomass and
Biofuels Syngas Natural
Gas Carbon Capture
Industrial Water
RTI International
Post-Combustion Capture Areas • Non-Aqueous Solvents • Advanced Solid Sorbents • Membrane Processes • Hybrid Processes
Pre-Combustion Capture Areas • Sorbents for warm CO2 removal from syngas • Integration of advanced CO2 capture processes
with RTI’s Warm Desulfurization Process
Carbon Capture R&D Activities at RTI
Water NAS
• Almost 15 years of continuous involvement in developing CO2 capture technologies
• Broad technology portfolio with significant activity in all major areas
• Building key capabilities in materials and process development
• Growing IP portfolio
4
RTI International RTI’s Carbon Capture (CC) Technologies
5
Non-Aqueous Solvents* (Post-CC)
Polymeric Membranes (Pre- & Post-CC)
Advanced Solid Sorbents* (Post-CC)
Warm CO2 Removal from Syngas* (Pre-CC)
* Highlighted in this presentation
Water NAS
Warm desulfurization enabling advanced CC process*
Advanced sorbents for warm CO2 removal from syngas
RTI International Post-Combustion (PC) CC Technologies Coal + Air CO2 + H2O + N2 + Contam. + Heat
• CC process is end of pipe (retrofit) • No/minimal changes to power plant • Key Challenges:
• Low CO2 concentration • 2-3 Million acfm of flue gas (550 MWe) • Contaminants • Integration with steam cycle
~12-15% CO2
~1% CO2
6
RTI International PC Capture – State of the Art
7
Mitsubishi Heavy Industries (MHI) & Southern Company MHI’s KM CDR Process® 150,000 tpy CO2 ~25 MWe
Technology Centre Mongstad (CO2TCM) • Aker Clean Carbon – Amine Plant • Alstom – Chilled Ammonia Plant • 100,000 tpy CO2 • ~20 Mwe - total
“Commercially-available” PCC Technologies1
All solvent-based process; Not demonstrated at scale • Fluor - Econamine FG+ Process • Mitsubishi - KM-CDR Process • Aker Clean Carbon – Just Catch Process • Cansolv – Cansolv CO2 Capture Process • Hitachi - H3 CO2 Capture Process • Toshiba – Toshiba CO2 Capture Process • Alstom/Dow – Advanced Amine Process • Alstom - Chilled Ammonia Process 1http://www.iea-coal.org.uk/documents/83086/8635/Coal-fired-CCS-demonstration-plants,-2012,-CCC/207
High thermal and electrical energy requirements Large quantity of high quality steam required for solvent
regeneration → derates low-pressure steam turbine Large compression energy requirement due to low CO2 partial
pressure generated during solvent regeneration → derates electrical generation
Parasitic power load ranges from 1,200 to 1,500 kJe / kg CO2
High capital and operating costs Expensive materials of construction due to corrosivity of solvents Extremely large process equipment High degradation rates due to O2 and SO2 in flue gas Evaporative losses and wastewater treatment requirements Large plant footprint
Rochelle, G. T. Amine Scrubbing for CO2 Capture. Science 2009, 325, 1652-1654.
Result: • Increase in Cost of Electricity (ICOE) > 65% • Cost of CO2 Avoided > $60 / tonne
Current USDOE Targets:
• ICOE <35% • Cost of CO2 Captured <$40/tonne
RTI International CO2 Capture Cost - R&D Focus
Breakdown of the Thermal Regeneration Energy Load
Sensible Heat Heat of Vaporization Heat of Absorption Thermal Energy Penalty
Solvent Cp [J/g K]
∆habs [kJ/mol]
∆hvap [kJ/mol]
Xsolv [mol solv./ mol sol’n]
∆α [mol CO2/ mol solv.]
Reboiler Duty [GJ/tonne
CO2] MEA (30%) 3.8 85 40 0.11 0.34 3.22
Lower Energy CC Process
Process capable of achieving these criteria will have a lower energy penalty than SOTA processes
8
RTI International
Absorber CO2-lean
solvent
Treated Flue Gas
CO2 Product Desirable Characteristics Favorable thermodynamics High working capacity Low heat of absorption Low regeneration temperature Low specific heat capacity Low vaporization of solvent
Low water solubility Low viscosity and high surface tension Low foaming tendency
Non-Aqueous Solvent CO2 Capture Process Post-Combustion Capture
Challenges Undesirable reactions with water Accumulation of water from flue gas in solvent Solids formation in rich solvent Viscosity, foaming tendency Solvent cost and availability Emissions in process water and treated flue gas
Aq. Amine Solvent NAS
9
Precipitation during absorption (Undesirable)
Formation of a second liquid phase
RTI International Non-Aqueous Solvent CO2 Capture Process
CO2-lean Flue Gas
Flue Gas from WFGD
Flue Gas Wash
CO2 A
bsor
ber
Rege
nera
tor
CondenserCO2 Product
To Compression Train
TrimCooler
CoolingWater
Low PressureSteam
CrossoverHeat Exchanger
CO2-leanSolvent
CO2-richSolvent
CO2 A
bsor
ber
Waste Water
Condensate
Make-up Water
CO2
Steam
• Technology in development at RTI since 2009
• Strong partnerships with government and industrial partners
• Comprehensive patent portfolio • 3 formulation related applications filed • 3 process related applications filed
RTI is developing a NAS CO2 capture process for post-combustion applications that has the potential to reduce the regeneration energy penalty to < 2.0 GJt / tonne CO2 (~40% < state-of-the-art solvents).
Treated FG
FG
10
RTI International
Previous Work DOE ARPA-E Project DOE NETL Project (Current) Future Development
Yr 2009-10 2010-13 2014-15 2016-20 2020+
TRL 1 2 3 4 5 6 7 8 & 9 Proof of
Concept/Feasibility Pre-Commercial Demonstration
NAS CO2 Capture Process: Technology Roadmap
Pilot-scale prototypical system demonstrated in a relevant environment (Future) • Large pilot system, ~ 1 MWe (20 tonnes/day), using real flue gas and a complete process unit • Collect critical process information to support detailed T&E assessments and scale-up efforts
Lab Scale Development (Previous) • Solvent screening to identify promising solvent formulations • Lab-scale evaluation of NAS Process • Preliminary technical and economic assessments
Small Pilot System / Relevant Environment Testing (Current) • Bench-scale testing with in a process unit with major process components • Demonstrate ≤ 2 .0 GJ/tonne CO2 using bench-scale system • Address process, environmental, and economic challenges • Detailed solvent degradation and emissions studies • Detailed Techno-Economic & EH&S Assessments
11
RTI International
NASs achieve larger dynamic capacities (∆α) with smaller ∆Ts CO2 pressure of > 2bar can be achieved around 90°C
CO2 Isotherms
Heat of absorption ranging from 55 to 75 kJ/mol CO2 Specific heat capacity of 1.2 to 1.5 kJ/kg K
Heat of Absorption
Why are RTI’s NASs so promising? Superior Thermodynamic Properties
12
RTI International
30 wt% MEA / Water NAS-2
CO2-Lean CO2-Rich
NAS Physical Properties
30 wt% MEA-water Solvent Foaming issues observed Failed test by expanding > 3x to overflow cylinder
NASs No foaming issues observed Very little retention of gas in solvent
13
Viscosity measured for CO2-lean and CO2-rich solvents at absorption (40°C) and regeneration (80°C) temp.
30 wt% MEA is reported to be 1.7 cP (lean) and 2.7 cP (rich) at 40°C1
Non-aqueous solvents have very reasonable viscosities and can utilize conventional gas absorption equipment
Measured Viscosity
Sample Name Viscosity [cP] Temp [°C]
NAS-1, CO2-Lean 4.5 40
1.6 80
NAS-1, CO2-Rich 20.7 40
NAS-2, CO2-Lean 7.2 40
2.5 80
NAS-2, CO2-Rich 27.1 40
RTI International
Demonstrated stability of non-aq. solvents in a representative process arrangement Evaluated/demonstrated key process concepts specific to non-aqueous solvent process
Water balancing; effectiveness of numerous regenerator types Compared performance of the NAS process and 30 wt% MEA-H2O
Prelim. data verifies 30-40% reduction in thermal regeneration energy Evaluated the effect of long-term (>500 h) exposure to common flue gas contaminants Supported design of small pilot unit for engineering-level evaluation of NASs
14
Small Bench-scale Testing
60
70
80
90
100
110
120
130
140
150
160
0
5
10
15
20
25
30
35
40
45
50
0 10 20 30 40 50 60 70 80 90 100
CO
2 C
aptu
re E
ffici
ency
& C
O2
Bal
ance
[%]
CO
2 C
once
ntra
tion
[vol
%]
Time-on-Stream [h]
CO2 ConcentrationCapture EfficiencyCO2 BalanceSample Collection
RTI International
Regeneration Energy & Technical Assessment
15
Several candidates identified that have potential to achieve regeneration energies < 2.0 GJt / tonne CO2
Note: Density of NASs is ~ 1.35-1.45 kg/L
RTI’s NASs
CO2 Capture Process
Net Power [kWe]
Net Efficiency
[%]
Efficiency Point Loss
No Capture* 784,700 39.3 - Fluor Econamine FG+* 549,970 28.4 10.9
RTI’s NAS Process 652,079 32.7 6.6
NAS CO2 capture process has potential to reduce parasitic power load by ~ 40% compared to MEA-based process
NAS Process requires lower quantity and quality of steam for solvent regeneration 40% less steam; upto 30oC cooler steam
Potential for significant reduction in increase in cost of electricity --- much more work needs to be done
Process modeling to estimate parasitic power load Thermal Regeneration Energy
* Cost and Performance Baseline for Fossil Energy Power Plants, Volume 1: Bituminous Coal and Natural Gas to Electricity (Nov 2010)
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
5,000
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Reg
ener
atio
n E
nerg
y [k
J t/k
g C
O2]
L/G [kg/kg]
30 wt% MEANAS 1NAS 2NAS 3NAS 4
2,500 kJt/kg CO2
2,000 kJt/kg CO2
3,680 kJt/kg CO2
1,700 kJt/kg CO2
Range of most advanced processes
RTI International
Project Objective: Continue the advancement of the NAS CO2 Capture Process • address specific challenges facing technical and economic potential • bench-scale demonstration of the potential to reduce the energy penalty to <2,000 kJt/kg of CO2 • understand potential for scale-up and demonstration at NCCC
Current Efforts: Bench-scale testing to demonstrate
≤ 2 .0 GJ/tonneCO2 Address process, environmental,
and economic challenges Detailed solvent degradation and
emissions studies Collect key performance data for all
major process units to estimate the size and cost of full-scale process components
Detailed Techno-Economic & EH&S Assessments
Next Development Steps
• Inventor of non-aqueous CO2 solvent chemistry
• Lead bench-scale testing campaign to optimize process performance
• Global leader in gas separations & purifications solutions
• Expertise in the design, engineering, and operation of gas treatment processes
• Techno-economic and EH&S assessments of novel processes
• Extensive experience in amine degradation & amine plant emissions
RTI International Advanced Sorbent CO2 Capture Process Post-Combustion Capture
17
Advantages • Potential for reduced energy consumption compared to
SOTA solvent processes • High CO2 working capacity compared to solvents • Reduced sensible heat load due to lower heat capacities • Steam stripping can be minimized / eliminated • Avoids evaporative emissions
• Potential for reduced capital costs through simplified process designs and inexpensive materials of construction
Challenges • Low-cost sorbent with high and stable working capacity
suitable for fluidized-bed processes • Effective heat management in absorber & regenerator • Pressure drop across sorbent bed • Sorbent make-up and particulate matter emissions
TCWS
TCWR
TCWS
TCWR
TCWS
TCWR
Flue Gas from Deep Desulfurization Wash
G [kg/h]
CO2 Absorber CO2-leanSorbent Feed
CO2-richSorbent Exit
S [kg/h]
Treated Flue Gas
RTI International
• Technology in development at RTI and PSU since ~2000
• Strong partnerships with government and industrial entities
• Current development efforts:
• transition a promising sorbent chemistry to a low-cost sorbent suitable for use in circulating fluidized-bed process
• bench-scale demonstration of complete circulating fluidized-bed process
Advanced Sorbent CO2 Capture Process RTI is developing a sorbent-based CO2 capture process that uses a supported, polymeric amine sorbent and a fluidized-bed process arrangement for post-combustion applications (power and industrial installations).
18
H--CH2-CH2-NH--Hn( )
Nano-porous Material
CO2/H2S-philic Polymer (Polyethylenimine)
“Molecular Basket” Sorbent (MBS)
+CO2-philic Polymer(e.g. Polyethylenimine)
Immobilize PEI into Nano-PorePolyethylenimine (PEI)
Promising sorbent chemistry
RTI International Sorbent Improvement
Reduce sorbent cost • Many supported sorbents being developed are experimental
materials with cost in the $1,000s / kg • Numerous low-cost, commercially-available support materials
have been identified • To-date 1,000x reduction in cost compared to mesoporous
silicas • Certain low-cost materials exhibit superior performance • Cost Target <$5/kg 0
2
4
6
8
10
12
14
65 75 85 95
CO
2Lo
adin
g [w
t% C
O2]
Absorption Temperature [°C]
MCM-41Trisyl p100FS
Absorption: 65C, 15% CO2, 5.6% H2O, 2.6% O2 Regeneration 110C, 5.7% H2O, N2 Aging: 120C, 90% CO2, 10% H2O for 10 hours
Sorbent performance improvement • Sorbent must be stable under realistic process conditions • Eliminate leaching of polymeric amine from porous supports
under process conditions • Mitigate / control oxidative degradation • Measure degradation rates with flue gas contaminants (SO2,
NOx, dust, HCl, etc.) and determine acceptable limits
19
RTI International Conversion to a Fluidizable Platform
20
Converted powder sorbents to low-cost, fluidizable, attrition-resistant particles suitable for use in a fluidized-bed process
• Spray Drying • Suitable particle size and density • Physically strong and resistant to attrition • Non-cohesive
Evaluation of fluidizability under process conditions • Lab-scale, visual fluidized bed constructed to evaluate prepared
sorbents at specific process conditions to allow for visual observation / characterization of the sorbent bed
Pilot-Scale NIRO Mobile Minor spray dryer
RTI International
• Staged, Circulating Fluidized-bed with Integrated Heat Management • evaluate effectiveness of staged reactor
design with integrated heat management system for CO2 removal from flue gas
• evaluate fluidizable, attrition-resistant, supported polymeric amine sorbent
• Specifications
• Flue gas throughput: 300 and 900 SLPM • Solids circulation rate: 75 to 450 kg/h • Sorbent inventory: ~100 kg of sorbent
• Mechanically completed • Field verification of instrumentation and
daq./control system (1st wk of 6/14) • Cold and hot flow verification (2nd wk of 6/14) • System operation with CO2 Sorbent starting 3rd
week of June 2014
Bench-scale Contactor Evaluation Unit
21
RTI International
22
Next Development Steps Process Demonstration at an Industrial Source
Demonstrate RTI’s advanced sorbent CO2 capture process in an operating cement plant
Norcem’s Brevik Cement Plant (Source: Norcem)
Project Team
Timeframe: 2 years [May ‘13 – Sept ‘15]
Project Scope Phase I – Current
• Feasibility study of RTI’s technology applied to a commercial cement plant through detailed economic evaluations
• Perform sorbent exposure testing real cement plant flue gas to demonstrate sorbent stability
Phase II • Optimize the sorbent preparation and reactor
designs for cement plant application • Detailed engineering, permitting, construction of pilot
system • Pilot field testing of technology at Norcem’s Brevik
cement plant
22
RTI International On-stream Testing at NORCEM
23
• Evaluate sorbent performance under realistic process conditions using real cement plant kiln gas
• Measure sorbent stability in presence of untreated kiln gas and treated kiln gas
• Acceptable contaminant levels for SO2 and NOx to be determined at RTI prior to testing at Norcem
• Multi-cycle stability – in excess of 200 cycles (this is arbitrary – need to find a better definition)
• Determine efficacy of pretreatment processes for removal of SO2 and NOx using real kiln gas
• >80 abs-des cycles on-stream so far • Currently awaiting cement plant restart
RTI International Pre-Combustion CO2 Capture – IGCC
Syngas produced via gasification of coal with purified O2 – Mixture of H2, CO, CO2, and H2O
Water-gas shift and CO2 removal to produce a H2-rich fuel gas – CO + H2O ↔ H2 + CO2
H2 is combusted to produce power
Integrated Gasification Combined Cycle (IGCC) Advantages • High chemical potential (T, PCO2) • Low Volume Syngas Stream • Commercially-available CO2 capture options
• e.g. Selexol™ • 30+ years of operation (55 worldwide
plants) • Highly selective for H2S and CO2
• CO2 is produced at pressure
Challenges • Complex, integrated & expensive power
process • Additional process (WGS) to achieve high
capture efficiency • Current technology (Selexol™) requires cooling
and reheating
Opportunities • Sorption Enhanced Water-Gas Shift (SEWGS) • Improved IGCC efficiency through CO2 capture
at elevated temperatures – no gas cooling
24
Coal + O2 + H2O H2/H2O + CO/CO2 + Contam.
RTI International
A unique process technology based on transport reactor design (related to Commercial FCC Reactor Designs]…
… based on the development of a highly active, attrition resistant sorbent.
RTI proprietary desulfurization sorbent • R&D 100 Award in 2004 • Developed through long-term
cooperation with Clariant Part of comprehensive high temperature contaminant removal platform.
RTI’s Warm Desulfurization Process Enabling Pre-Combustion CC Technologies
25
RTI’s Warm Desulfurization Process (WDP) has been developed to remove sulfur compounds (H2S, COS, CS2, mercaptans) from syngas to ~ 1ppm-levels at > 350oC.
RTI International
>20 year development timeline with numerous stages & partners
RTI’s Warm Desulfurization Process Enabling Pre-Combustion CC Technologies
26
Demonstration (2010-2015): Syngas cleanup / carbon capture • Tampa Electric IGCC Plant, Florida • $168.8MM DOE funding to design, construct, operate • 50 MWe equivalent scale
Invention (2001) • Proprietary desulfurization sorbent • R&D 100 Award (2004)
Pilot testing (2006-2008) • Eastman Chemical Co. • 3000hr, coal-derived syngas
Lab/bench testing (2001-2003) • RTI • Concept proven & modeled
Technology Team RTI BASF Tampa Electric Clariant Shaw Group, AMEC DOE/NETL CH2M Hill Eastman Chemical
Large teams/partnerships are necessary to complete projects at this scale & beyond
RTI International
Source: BASF
CO2 Capture: BASF aMDEA® Process
Activated MDEA (aMDEA®) • aMDEA® has the lowest specific energy consumption
of any standard amine solvent for CO2 removal.
• aMDEA® has higher absorption kinetics and capacity reducing equipment size resulting in lower capex and opex.
• Extensively used in hydrogen production, ammonia manufacture, cryogenic gas processing, and LNG production
• Exploiting aMDEA® for CCS in IGCC requires selective sulfur removal technology
RTI’s Warm Desulfurization Process (WDP) enables use of advanced CC technology previously not used for this application.
Feed Gas CO2, H2S aMDEA
27
RTI International
Integration of Syngas Cleaning and Carbon Capture Systems at Tampa Site
Clean Fuel Gas
Process Water
20% slipstream test (~50 MWe) enables direct commercial scale-up from this demonstration scale
Air
Air Separation
GE Gasifier (400 psig)
Syngas Cooling Scrubbers COS
Hydrolysis
Oxygen
Coal/Petcoke
Char
Syngas Cooling MDEA
Sulfuric Acid Plant Sulfuric
Acid
Process Condensate
Reheat/ Humidify
Clean Fuel Gas Slag
Acid Gas
Syngas Diluent (N2)
128 Mwe (122 Mwe)
8% H2O Extraction Air
~
~
Water Gas Shift Reactor WDP Syngas
Cooling aMDEA CO2 Recovery
Regenerator Gas
Project Scope
Raw Syngas
Currently vented, but could be sequestered or
recycled
WDP enables advanced CC technology previously not used for this application
28
RTI International RTI’s 50 MW Demo Project Demonstrate RTI’s technology to reduce capital costs, improve efficiency, and lower the carbon
footprint of advanced gasification Mitigate design and scale-up risks for the first commercial plant Obtain 5,000 to 8,000 hours of operations Determine performance metrics Verify capital and operating costs Validate start-up and shut-down procedures
Capture >90% of CO2 in syngas ~1,000 tonnes CO2 / day
50 MW Installation at TECO [Nov. 2013] 29
RTI International Completed Construction & Currently on Syngas
March 19, 2014
RTI International Our experience with CCS at Tampa Electric Designed and built a carbon capture system
equivalent to a 50 MWe plant Characterized the geology for on-site storage Determined that Polk Power Station (TECO) is
located above a suitable aquifer Modelling indicated rapid mineralization of CO2
and found synergies with waste water injection
EPA originally granted a Class V well permit but later insisted on Class VI permit – Class V: Inject non-hazardous fluids underground – Class VI: Injection of CO2 into underground
subsurface rock formations for long-term storage, or geologic sequestration.
50 year MVA requirement Clarified and expanded financial responsibilities Project team decided to not sequester CO2
since responsibility & liability would exceed project lifetime
31
RTI International
Banholzer, 2008
CO2 Utilization
32
CO2 Properties Fully oxidized form of carbon Extremely chemically stable Conversion to useful products requires abundance of
reducing agents and energy Challenge Low-cost, abundantly available reducing agents that
have a small CO2 footprint Large enough market to mitigate CO2 emissions Cost-effective (competitive) pathways to valuable
products
Potential pathways that RTI is developing • CO2 to CO using pet-coke and waste chars
CO2 + C 2CO [Reverse-Boudouard Reaction]
• Ethylene epoxidation
RTI International Acknowledgements
33
Strategic Partners • U.S. Department of Energy
• Office of Fossil Energy - National Energy Technology Laboratory (NETL)
• Advanced Research Project Agency – Energy (ARPA-E)
• U.S. EPA
• Gassnova – The Norwegian state enterprise for
carbon capture and storage.
• Commercial Partners • BASF • Linde • Masdar • Norcem • SINTEF
• University Collaborators
• Pennsylvania Sate University • Masdar Institute
Key RTI Staff Contributing to CO2 Program • Dr. Marty Lail • Mr. Thomas Nelson • Dr. Atish Kataria • Dr. Markus Lesemann • Dr. Jak Tanthana • Dr. Paul Mobley • Dr. JP Shen • Dr. Sree Pavani • Dr. Brian Turk • Dr. Raghubir Gupta
RTI’s Energy Technology Division
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