1 www.rti.orgRTI International is a registered trademark and a trade name of Research Triangle Institute. www.rti.orgRTI International is a registered trademark and a trade name of Research Triangle Institute.

RTI Warm Syngas Cleanup Technology Demonstration8th International Freiberg Conference on IGCC & XtL Technologies

June 13, 2016David L. Denton (speaker),

Raghubir Gupta, Markus Lesemann, and Brian Turk

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What Is RTI International?

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.

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Energy Technology DivisionRTI InternationalTurning Knowledge Into Practice

4,150 staffWork in 75 countries

3,680Active projects

Scientific staffHighly qualified, tremendous breadth

$831.5 millionResearch budget

One of the world’s leading research organizations

RTI and Its Energy Technology Focus

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RTI Warm Syngas Cleanup Technology Platform

Flexible modular approach enables specific syngas purity needs to be met

Systems tested on actual coal-based syngas

Warm desulfurization process (WDP) now tested through pre-commercial scale

Increase efficiency and lower costs

Operate at 250-600ºC

Pressure independent

Effective for all forms of sulfur

Fully compatible with all CO2 capture

RTI PILOT PLANT TEST UNITS ATEASTMAN COAL GASIFICATION PLANT

PRE-COMMERCIAL DEMO PROJECT w/CCUNDERWAY AT TAMPA ELECTRIC SITE

Hg adsorbents (disposable)

As adsorbents (disposable)

Regenerable CO2 sorbents

SulfurRegenerable ZnO sorbents

Transport reactor

Direct Sulfur Recovery Process

Regenerable NH3/HCN adsorbents

HCl adsorbents (disposable)

Se adsorbents (disposable)

RTI has developed a platform of warm syngas cleanup technologies:

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RTI Warm Gas Desulfurization Process (WDP)

A unique process technology based on dual transport reactor loops (similar to FCC reactor designs)…

… and on the development of a highly active, attrition-resistant sorbent.

REGENERATED SORBENT TO ADSORBER MIXING ZONE

REGENERATEDSORBENT

RAW SYNGAS

CLEAN SYNGAS

N2/O2(Air)

SO2 / N2TO SULFURRECOVERY

RTI Warm Gas Desulfurization Process (WDP)

250-650°CADSORBER(REACTOR)

650-750°CREGENERATOR

(REACTOR)

Enables high removal of total sulfur (>99.9%) from syngas at temperatures as high as 650°C.

RTI Proprietary Desulfurization Sorbent R&D 100 Award Unique highly-dispersed

nanostructures Developed in long-term

cooperation with Clariant (~100 tons to date)

Covered by extensive US & International patents, including several recent improvements

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Successful WDP Scale-up from Lab to Large-Scale Pre-Commercial Testing

Invention (2001) • Proprietary RTI sorbent • High attrition resistance

Lab/bench testing (2001-2003)• RTI International, NC• Concept proven & modeled

Pilot testing (2006-2008)• Eastman Chemical Co., TN• >3000 hr coal-based syngas

Pre-Commercial – Syngas Cleanup & CO2 Capture (2010-2016)• Tampa Electric Co., Polk 1 IGCC Plant, FL• 50-MWe scale, >3500 hr with coal/petcoke-based syngas

Over 6500 hours of combined pilot and pre-commercial scale testing of WDP!

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Demonstration Project Team Role

RTI Project management; technology developer

Tampa Electric (TEC) Host site, feed, utilities, operations support

Shaw Group, AMEC Engineering (Shaw - FEED, AMEC - EPC)

CH2M Hill Owner’s engineer

BASF Technology (aMDEA® ) for CO2 capture

Clariant Supply of sulfur sorbent & WGS catalysts

DOE/NETL Funding agency; project consultation

Eastman Chemical Development partner; early tech support

CO2 Capture

WGS Reactors

RTI WDP 50-MWe Pre-Commercial Demonstration Testing Project

Project Detail: Combined syngas cleanup / water-gas-shift / carbon capture demonstration• DOE ARRA funding to support the design, construction, and operation• 50 MWe equivalent scale - 20% slipstream from TECO Polk 1 IGCC unit; captures > 90% of CO2

Desulfurization System

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Overall Objective for WDP Pre-Commercial Operational Testing

The overall objective of this project was to mitigate the technical risks associated with the scale up and integration of the warm syngas cleaning and carbon dioxide (CO2) capture

technologies, enabling subsequent commercial demonstration.

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Integration of Syngas Cleaning and Carbon Capture Systems at Tampa Electric Company Polk 1 IGCC Site

Clean Fuel Gas

Process Water20% slipstream test (~50 MWe) enables direct commercial scale-up from this pre-commercial scale.

The WDP test facility cleans ~2MMscfh (~70,000 Nm3/hr) of raw syngas from the TEC gasifier.

Air

AirSeparation

GE Gasifier(~400 psig)

SyngasCooling Scrubbers COS

Hydrolysis

Oxygen

Coal/Petcoke

Char

SyngasCooling MDEA

SulfuricAcid Plant Sulfuric

Acid

Process Condensate

Reheat/Humidify

Clean Fuel GasSlag

Acid Gas

Syngas Diluent (N2)

128 Mwe(122 Mwe)

8% H2OExtraction Air

~~

Sweet WGS ReactorsWDP Syngas

Cooling aMDEA® CO2Recovery

Regenerator Gas

Pre-CommercialProject Scope

Raw Syngas

Currently vented, but could be sequestered or

used or recycled

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Construction was achieved on schedule and under budget. ~600,000 total construction and operation labor hours with

no injury other than a few minor first aids. Unit performed as expected, replicating previous lab and

pilot scale performance. RTI WDP unit consistently reduced inlet total sulfur from as

high as 14,000 ppmv (40% over design level) to ~10-20 ppmv or less (~99.9% removal).

Clean syngas exiting the activated amine (aMDEA®) carbon capture block was consistently <0.5 ppmv (as low as 100 ppbv, ~99.999% total S removal).

Microreactor testing of the cleaned syngas (post-aMDEA®) with commercial Fischer-Tropsch (Fe- and Co-based) and methanol catalysts showed no significant signs of catalyst deactivation after several hundred hours of testing.

WDP Unit

RTI Warm Gas Cleanup (WDP) Pre-Commercial Testing Project Performance

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RTI Warm Gas Cleanup (WDP) Pre-Commercial Testing Project Performance

Sorbent attrition rate was better (lower) than design expectations.

Sorbent sulfur capacity was steady - no significant deactivation was observed.

WDP unit was successfully operated both below and above its design syngas feed rate and design sulfur feed rate.

RTI achieved >3,500 total syngas operation hours on WDP, >2,000 hrs on WDP+aMDEA®, and ~700 total integrated hours on WDP+WGS+aMDEA® by the end of testing.

WDP availability at the end of testing was as high as 93% and identified design improvements should enable availabilities in the high 90’s% for future commercial units.

RTI is now in discussions with potential partners to offer the technology (via license) and sorbent (via sale) commercially later this year.

WDP Unit

DOE/RTI/TEC/Clariant Team

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Pre-commercial Demonstration Test Plant Results: Consistently High Total Sulfur Removal (H2S and COS)

Four months of WDP operations

• H2S Removal (inlet H2S = 10,000-12,000 ppmv)• COS Removal (inlet COS = 600-900 ppmv)

Note: Gaps are due to periods of syngas outages

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Comparison of Technologies for Syngas Sulfur Removal and CO2 CaptureCharacteristics Rectisol® Selexol™ RTI + aMDEA®

Capture Mechanism Physical absorption Physical absorption Solid adsorbent + chemical absorption

Pressure Dependent? Yes Yes No (for S removal)

COS Hydrolysis Needed? No Yes (most applications) No

Operating Temperature -40°F to -80°F 30°F to 100°F S removal: > 600°FCO2 capture: ~110°F

Sulfur Removal < 0.1 ppmv H2S + COS

< a few ppmvH2S + COS

~ 0.1-0.5 ppmv H2S + COS

(< 0.1 ppmv w/guard bed)

CO2 Capture 97-99% 90-99% > 97%

Relative Efficiency w/CO2Capture

< X% (due to refrigeration) X% Can be up to 10% higher

Relative Capital Costs > Y (pressure dependent) Y 20-50% lower

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RTI WDP Provides Significantly Lower Capex and Opex !

Technology used in RTI Demo Plant

NOTES: • Cost savings are across the entire block from raw warm syngas exiting the gasifier through

cleaned syngas feed to the methanol conversion step, including the sulfur recovery unit. • These analyses do not include additional benefits to the entire plant that might occur from

overall efficiency savings.

Non-labor, non-feedstock operating costs

RTI WDP improves

economics for all carbon

capture options, but best when coupled with

activated amine.

Techno-Economic Analysis (TEA): Coal to Methanol Case (2 x 300-MWequiv Shell-type solids-fed gasifiers with Shenhua Mix or PRB coal)

OPEX reduced

>50%

Rectisol®Base Case

RTI WDP + Rectisol®

RTI WDP + Selexol™

RTI WDP + aMDEA®

CAPEX reduced ~50%

Rectisol®Base Case

RTI WDP + Rectisol®

RTI WDP + Selexol™

RTI WDP + aMDEA®

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100%

-500%

Single-Stage Selexol™

RTI WDP reduces AGR OPEX*

RTI WDP

100%

55%

Dual-Stage Selexol™ RTI WDP + aMDEA®

RTI WDP reduces AGR OPEX*

100%

67%

Dual-Stage Selexol™ RTI WDP + aMDEA®

RTI WDP reduces AGR CAPEX

100%

79%

Single-Stage Selexol™ RTI WDP

RTI WDP reduces AGR CAPEX

WDP Economic Benefits for IGCC Power Generation Cases (2 x 300 MWe Shell-type gasifiers w/PRB or Shenhua Mix coal)

* Non-labor, non-

feedstock OPEX

IGCC w/oCarbon Capture

IGCC with90%

Carbon Capture

CAPEX and OPEX are for AGR + WGS

+ LTGC + SRU blocks

Note:The capex savings shown here are for the entire syngas cleanup block, but do not include additional savings for the overall IGCC due to improved efficiency. The overall IGCC capex savings can more than offset all WDP cleanup capital costs for IGCC w/o carbon capture or for IGCC with a warm carbon capture process.

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Benefits of RTI WDP Technology Rectisol® and Selexol™ (solvent-based sorbent systems that operate at sub-

ambient temperatures) dominate the current coal-to-chemicals/fuels markets.

RTI WDP is a unique differentiated warm-temperature, solid-sorbent based syngas cleanup system that simultaneously offers:– Lower capital costs (20-50% less),

– Lower non-labor, non-feedstock operating costs (up to 30-50+% less),

– Improved overall process efficiency (up to 10+% better),

– Improved process flexibility by decoupling sulfur removal and CO2 capture, and

– A capable and economic syngas cleanup option for all applications:

CC = Carbon Capture

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Summary RTI’s warm syngas cleanup technology offers opportunities to both improve efficiency and

significantly reduce capex/opex costs of gasification for power generation and chemicals/fuels.

RTI’s WDP has potential to integrate with most CO2 capture technologies (e.g., amines, activated amines, Selexol®, Rectisol®, sorbents) to enable them to meet syngas purities for chemicals/fuels applications and for ultra-clean power generation with competitive economics.

The WDP pre-commercial (50-MWe) testing program was a success and the unique transport system design and sorbent combination performed as expected, replicating previous lab and pilot scale performance and providing critical data to support full-scale commercial deployment.

RTI WDP was integrated with an aMDEA® carbon capture system and total sulfur levels dropped to sub-ppmv levels (up to 99.999% removal), performance levels needed for most chemicals/fuels applications as validated by microreactor testing with commercial FT and methanol catalysts.

RTI WDP technology performance has been consistently proven at lab, bench, pilot plant (>3,000 syngas operation hours), and pre-commercial scales (>3,500 syngas operation hours).

RTI is now in discussions with potential partners to offer the technology (via license) and sorbent (via sale) commercially later this year.

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Acknowledgements

RTI Co-Authors/Contributors

U.S. Department of Energy / National Energy Technology Laboratory for Funding Support

Development and Project Partners:– Tampa Electric Company

– Eastman Chemical Company

– Technip

– Amec Foster Wheeler

– CH2M Hill

– BASF

– Clariant

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Contact: David DentonSr. Director, Business DevelopmentEnergy Technology DivisionRTI Internationalddenton@rti.org919-485-2609 (W), 423-384-6217 (M)

QUESTIONS?

RTI Warm Syngas Demonstration Project