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

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RTI International RTI’s Carbon Capture (CC) Technologies

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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

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RTI International PC Capture – State of the Art

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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

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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

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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

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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

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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

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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

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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

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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

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Small Bench-scale Testing

60

70

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90

100

110

120

130

140

150

160

0

5

10

15

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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

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Regeneration Energy & Technical Assessment

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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

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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).

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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

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RTI International Conversion to a Fluidizable Platform

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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

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RTI International

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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

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RTI International On-stream Testing at NORCEM

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• 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

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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

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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

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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

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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

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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

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RTI International

Banholzer, 2008

CO2 Utilization

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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

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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