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Putting enzymes to work™

ADVANCED LOW ENERGY ENZYME-CATALYZED SOLVENT FOR CO2 CAPTURE

John Reardon; Director, Engineering Project: DE-FE0004228 NETL National CO2 Capture Technology Meeting; Pittsburgh, PA July 9, 2013

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Company profile and project overview

Technical background & fundamentals

Progress and current status

Summary of results

Future work

OUTLINE

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• St. Louis-based biotechnology company

Developing lower cost, environmentally friendly solutions for CO2 capture for variety of applications

• Integrating proprietary biocatalyst delivery with various solvent systems

Company profile

AKERMIN INC.

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Project awardee, FFRDC, and Subcontract:

Enzyme Supply:

Test Site: (NCCC) Fabrication:

Project duration: 36 months (Oct 2010 to Sept 2013)

Funding

Participants, Duration, Funding

PROJECT OVERVIEW

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DOE Funding: $ 3,275,043 Akermin Cost share: $ 2,881,695 Total Project: $ 6,156,738

Instrumentation:

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Putting enzymes to work™

TECHNICAL BACKGROUND AND FUNDAMENTALS

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Indicative temperatures and pressures “simple solvent system”

SCHEMATIC BASIC OPERATION

*Temperatures shown here are indicative of ~ adiabatic scenario using potassium carbonate regenerated at near ambient pressure.

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BIOCATALYST

*Vacuum blower: Leverage low quality steam to reduce equivalent work

VBLR

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Coated packing: Akermin’s first generation biocatalyst delivery system

CORE TECHNOLOGY FOR THIS PROJECT

Proprietary formulation achieves high activity and stability

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ENZYME

SOLUTION OF MONOMERS AND ADDITIVES

ENZYME SUSPENSION

COATING

ASSEMBLY

SEM IMAGE OF COATING

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CA accelerates hydration of CO2 to bicarbonate:

Base captures proton to complete reaction

Akermin explored numerous CAs

CA developed by Novozymes is top candidate Highly active

Resistant to major impurities in flue gas

Thermostable

Resistant to high pH (9-10.5)

High expression level, few impurities

CHEMISTRY: CA-CATALYZED CO2 ABSORPTION

Key point: CA mechanism is potentially applicable in many basic solvent systems

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kcat = 106/sec

Active site of CA

𝐻2𝑂 + 𝐶𝑂2 ⇌ 𝐻+ + 𝐻𝐶𝑂3−

CA

𝐵 + 𝐻+ ⇌ 𝐵𝐻+

CA: Carbonic Anhydrase

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Reducing column height enables certain solvent systems to become feasible

CATALYST REDUCES COLUMN PACKED HEIGHT

Goal: > 10X overall improvement in packing height

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BLANK (1X) 4X Improved 10X Improved 16X Improved Equilibrium

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The most effective and scalable method of CO2 capture from flue gas is via chemical reaction

BENEFITS OF TECHNOLOGY TO THE PROGRAM

Technology broadens the choice of solvents to be used in CO2 capture

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Both CCS cases include a $5.7 /MWh charge for CO2 Transport, Storage and Monitoring

Estimated Costs of Greenfield Super Critical PC Power Plant with CO2 Capture

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Achieve long-term stability

Minimize inhibition by flue gas impurities

Maximize enzyme retention, minimize leaching

Maximize activity (minimize diffusion resistance)

Replenishment of enzyme with minimal interruption

TECHNICAL CHALLENGES

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Putting enzymes to work™

PROGRESS AND CURRENT STATUS

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Installed at NCCC December 2012

BENCH UNIT CURRENTLY OPERATING AT NCCC

Sulzer M500X 8.33” ID x 26 ft packing Gas: 30 Nm3/hr Liquid: 275 LPH

Blank testing complete

Immobilized enzyme installed and has been operating since May 2013

Planning to operate through end of September 2013.

Instrumentation and controls:

Module Design and Fabrication:

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Data at design flow (31.5 Nm3/hr, 275 LPH, XCL ~ 25%)

BENCH UNIT DATA WITH BIOCATALYST

More than 1250 Hrs On Steam as of 7/09/2013, and continues.

Average CO2 inlet ~ 12% (dry basis)

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100 300 500 700 900 1100 1300

CO

2 C

aptu

re (

%)

Time On Stream (hours)

NETL-Akermin CO2 Capture System at NCCC

Parametric Testing Parametric Testing

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Biocatalyst achieved (average) 90.1% CO2 capture with ~20 Nm3/hr flue gas flow

compared to blank estimated ~2.8 Nm3/hr flue gas flow at 90% capture.

90% CO2 CAPTURE TEST (~20 SCMH)

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100

216 218 220 222 224 226

CO

2 C

aptu

re (

%)

Time On Stream (hr)

~7-fold higher gas flow achieves 90% capture with biocatalyst compared to without biocatalyst in the current column

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Component HSS

(mg/L)

Rate moles/L

/year

Loss of Solv. Capacity

(%/year)

Nitrite (NO22-) 25.1 0.0283 0.83%

Nitrate (NO3-) 6.41 0.0054 0.16%

Sulfate (SO42-) 36.1 0.0195 1.14%

Total 67.6 0.0532 1.55%

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PRELIMINARY (1 week of data), additional results pending

QUANTIFIED HEAT STABLE SALT ACCUMULATION

Preliminary estimate < 2%/year loss in capacity by HSS. Additional data and analytical results are pending.

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Component Sample #1 Sample #2

O2 ND ND

Ar+ O2 0.01% 0.01%

N2 0.01% 0.01%

Net CO2 99.98% 99.98%

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NCCC sampled CO2 product and analyzed purity with Gas Chromatography

QUANTIFIED CO2 PURITY: ~99.98%

High selectivity is clearly demonstrated with a high purity product

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Five Key Areas of Heat Loss Affecting Reboiler Duty (Temperatures displayed in °C)

HEAT LOSSES ON BENCH-SCALE PLANT

Combined effects of heat loss result in higher reboiler duties than could be achieved under adiabatic conditions (e.g., larger scale)

Heat loss on flue gas feed impacts Trich solution here

Long steam line with low flows impacts steam quality

Heat loss from reboiler line results in lower maximum approach temperature

Heat loss on riser reduces Trich feed to STR

Reboiler and Stripper Heat Losses ~0.6 kW

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This plot used for comparing Aspen prediction and regeneration energy data at test condition

VACUUM REGENERATION: ASPEN VS. DATA

Aspen model agrees within ~ 2.5% of measured values.

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5.0

5.2

5.4

5.6

5.8

6.0

6.2

6.4

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

Spe

cifi

c R

eb

oile

r H

eat

Du

ty (

GJ/

t CO

2)

Reboiler Pressure (bara)

Aspen Energy Prediction

Pilot REB Duty

REB-1 Pres. ΔT Hot

Approach Lean Loading Rich Loading

bara °C mol/mol K2CO3 mol/mol K2CO3

1.030 20.6 0.291 0.645 0.860 20.4 0.319 0.645 0.631 17.4 0.324 0.650 0.470 14.3 0.349 0.673 0.308 11.1 0.386 0.697

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ENERGY & EQUIVALENT WORK VS. REBOILER TEMP.

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• ~3.5 GJ/tCO2 with K2CO3, basic flow sheet

• Equivalent work < 150 kWh/ t CO2 for Steam + VBLR to 1.6 bar

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60 65 70 75 80 85 90 95 100 105

Equ

iv.

Wo

rk (

kWh

/t C

O2)

Reboiler Temperature (°C)

3.0

3.2

3.4

3.6

3.8

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Re

bo

iler

He

at D

uty

(G

J/t

CO

2)

Reboiler Temperature (°C)

0.25 XC (Lean)

0.30

0.35

0.30 (no kinetic limitation)

Using lower grade steam reduces the loss of power-generating capacity for the plant!

0.25 XC (Lean)

0.30

0.35

0.30 (no kinetic limitation)

Equiv. Work (Steam + VBLR) Reboiler Heat Duty Lower temperature regeneration reduces parasitic load at plant

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Demonstrated that significant acceleration of CO2 capture is achieved with immobilized CA in the absorber

Demonstrated 90% capture using K2CO3 salt solution

Demonstrated > 1200 hours online with no detectible decline in performance

Negligible heat stable salts accumulation

>99.9% purity of CO2 product

Near zero aerosol formation

30% - 50% reduction in equivalent work of steam regeneration, including vacuum blower

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SUMMARY OF RESULTS

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Complete TEA with PNNL (this project)

Beyond this project:

Scale-up, automate, and optimize manufacture of immobilized enzyme

Develop and demonstrate second generation replaceable enzyme delivery system

Demonstrate alternative solvents to further reduce regeneration energy and to lower equivalent work

Explore alternative biocatalyst-enabled flow sheets

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Outside of this project

FUTURE WORK

Wrapping up current project with final TEA and report.

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ACKNOWLEDGMENTS

US DOE-NETL Andrew Jones, Project Manager

Novozymes Generous supply of carbonic anhydrases

National Carbon Capture Center Test site and on-site operations support

PNNL Charles Freeman, Mark Bearden, James Collette, Dale King

Battelle Bradley Chadwell, Marty Zilka

EPIC Systems Inc: Module design, fabrication, controls programming

Emerson: Instrumentation and controls

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DOE/NETL: This material is based upon work supported by the Department of Energy National Energy Technology Laboratory under Award Number DE-FE0004228. Disclaimer: This presentation was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency.

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