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Putting enzymes to work™

Alex Zaks, Ph.D.Akermin, Inc. 

October 7th, 2014

INTERNATIONAL CONFERENCE ON GREENHOUSE GAS TECHNOLOGIES

Low energy CO2 capture enabled by biocatalyst delivery system

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DOMINANT APPROACH FOR CO2 CAPTURE TODAY: CHEMICAL ABSORPTION WITH AMINES

High operating costs & poor environmental profile Increases energy requirements Relies on volatile solvents Generates hazardous by‐products Accompanied by solvent degradation

Inadequate for large‐scale CO2 capture from flue gas streams

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Where does it fall short?

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ALTERNATIVE SOLVENTS

The use of K2CO3 requires a catalyst

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Solvent Characteristics Baseline(Amines) K2CO3

No amine aerosol emissions X

Non‐volatile (No VOC or HAPs) X

Non toxic X

High Capture Rate X

Oxidative stability X

Low viscosity X

Low corrosion X

Limited flue gas polishing needed X

K2CO3 is kinetically slow but otherwise highly attractive solvent

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Interconverts CO2 and HCO3‐ to maintain acid‐base 

balance and transport CO2 out of tissues.

A family of ubiquitous  enzymes Mammals, aquatic organisms, insects, plants, 

fungi, bacteria and archaea 

Active site contains metal (Zn2+)

MW  ~ 30,000Desirable characteristics: Thermostable Resistant to high pH (9.5‐10.5) Expressed at high levels with few impurities

CARBONIC ANHYDRASE: NATURE’S PERFECT CATALYST

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CHALLENGE

How to make a biocatalyst evolved in nature work under industrial conditions with following stressors:

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Enzyme optimization and advanced delivery is critical

Temperature (40‐ 105 oC) Extreme pH (9.8‐10.2) Impurities (SOx, NOx, etc.) Shear Forces Multiphasic systems

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AKERMIN’S BIOCATALYST DELIVERY SYSTEM

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Successful biocatalyst  approach enables: • Non‐toxic, non‐volatile solvent(s)• Novel process schemes

Enzyme

Protected from inactivation  in proprietary polymer film

High surface area polymer films enable 

higher mass transfer rate

Coated packing 

Micro‐particles

Options for biocatalyst delivery

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Installed at NCCC December 2012FIELD PILOT UNIT DEMONSTRATION

8.33” ID x 26 ft packingGas: 30 Nm3/hrLiquid: 275 LPH

Unit with immobilized enzyme operated May –Oct 2013 

Sulzer M500X

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FIELD TRIAL: LONG‐TERM PERFORMANCE 

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6 months

Minimum Achievable Now Projected

1 yearCommercial

Readiness Goal

2 yearsLIFETIME

9 months 18 months

Half‐life 539 days

2,800 hours on CO2 steam with 99% availability

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0

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20

30

40

50

60

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80

90

100

0 1 2 3 4 5 6 7 8

CO2Ca

pture (%

)

Test Time (hours)

19.4 m3/h of gas20.1 m3/hr of gas

Column with biocatalyst can handle ~7‐fold higher gas flow than that without biocatalyst to achieve 90% capture

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FIELD TRIAL: DEMONSTRATION OF 90% CAPTURE

90% capture with immobilized enzyme is achievable

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~3.4 GJ/tCO2  with K2CO3, basic flow sheet

3.03.23.43.63.84.04.24.44.64.85.0

60 65 70 75 80 85 90 95 100 105

Rebo

ilerH

eat D

uty (GJ/t C

O2)

Reboiler Temperature (°C)

0.25 (Lean)

0.30

0.35

0.30 (no kinetic limitation)

IMPACT OF KINETIC LIMITATIONS ON REBOILER DUTY OPERATED WITH KHCO3

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High CO2 loading  Low regeneration energy Non‐volatile Low EH&S risks Low molecular weight Thermally stable Highly water‐soluble Manufacturing route established Used in the past for gas treating

CHALLENGE: HOW TO FURTHER MINIMIZE ENERGYSecond generation solvent, AKM24

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LONG‐TERM PERFORMANCE OF THE PILOT WITH K2CO3 AND AKM24

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Long‐term stability with both solvents demonstrated

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20

30

40

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60

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80

90

100

100 600 1100 1600 2100 2600 3100 3600

CO2Ca

pture (%

)

Time On Stream (hours)

12% CO2 – K2CO3 4% CO2 – K2CO3

4% CO2 – AKM‐24

12% CO2 – AKM‐24

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SPECIFIC REBOILER DUTY FOR K2CO3 AND AKM‐24

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AKM‐24 is estimated to achieve 30% reduction in reboiler heat duty

2.0

2.5

3.0

3.5

4.0

4.5

5.0

60 70 80 90 100 110 120

Specific Re

boiler D

uty (GJ/t C

O2)

Reboiler Temperature (°C)

AKM‐24: Blank

AKM‐24: 15X 

K2CO3, Blank

K2CO3, 15X 

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CHALLENGE: HOW TO REPLENISH BIOCATALYST AT COMMERCIAL SCALE?

Recirculation within absorber only (requires particle separation) 

Continuous recirculation in absorber and stripper (req. lower temp. stripping)

Particle flow(Filter)

Two concepts employing enzyme delivery as micro‐particle:

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NEW PROJECT SUPPORTED BY U.S. DEPARTMENT OF ENERGY

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$3 million award;  work initiated in Oct’13

Goals  Demonstrate delivery of 

enzyme on micro‐particle  Complete characterization of 

AKM24 Test advanced system design Further reduction of energy 

and capital costs

• FOCUS ON MICRO‐PARTICLE• RECIRCULATIONTHROUGH ENTIRE

SYSTEM

• AKM24

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ENHANCEMENT FACTOR FOR GEN‐1 (PACKING) AND GEN‐2 (MICRO‐PARTICLES)

0

5

10

15

20

25

30

Enha

ncem

ent Factor 

(Normalize

d to 25°C K 2CO

3) 20 wt% K2CO3, 25°C

Gen 1A Biocat., 45°C

35 wt% AKM24, 25°C

Gen 2B Biocat. (0.75 wt%),  40°C

30 wt% MEA, 0.25 mol/mol, 40°C

30 wt% MEA, 0.35 mol/mol , 40°C

20 wt% K2CO3 35 wt% AKM24 30 wt% MEA

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Micro‐particles specifically designed to partition to gas‐liquid interphase  

Micro‐particles demonstrate a significantly higher acceleration potential than coatings

MEA

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373

281

238219 215

0

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300

350

400

Case 12 R230% MEA

20% K2CO385°C Reb

AKM‐24Case 1A60°C Reb

AKM‐24Case 2A80°C Reb

AKM‐24Case 2B105°C Reb

Total Equ

ivalen

t Work (kWh/ t CO

2)

CO2 Compression WorkVacuum Pump WorkReboiler Eq. WorkCirc. Pumps WorkID Fan Work

COMPARISON OF TOTAL EQUIVALENT WORK FOR VARIOUS CAPTURE SYSTEMS

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Potential of  reducing total equivalent work by 42% compared to Case 12

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INCREMENTAL COST OF ELECTRICITY (ICOE) FOR VARIOUS CAPTURE SYSTEMS RELATIVE TO NETL CASE‐11

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~ 33% reduction in ICOE appears to be achievable

66.362.0

58.0

45.8 43.9

 $‐

 $10

 $20

 $30

 $40

 $50

 $60

 $70

NETL Case 12.230% MEA

Gen. I20% K2CO3

Gen. IIAKM‐24Case‐1A

Gen. IIAKM‐24Case‐2A

Gen. IIAKM‐24Case‐2B

ICOE, 2011 Ba

sis ($/ M

Wh)

Fuel Cost Power Plant Capital CO2 Unit Capital Plant ChemicalsPlant Labor & Taxes Enzyme Cost TS&M

60 oC reboiler 105 oC reboiler80 oC reboiler

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Size: 500 Nm3/hr. biogas (50% of avg. commercial unit)

$7 MM, three year project50% funding through EUDP (Danish Energy Agency)Schedule: Project Kickoff – Jan 2014 Commissioning – May 2015 Operations – July 2015

24 months operation and testing

Commercial scale Biogas treating unit

FUTURE WORK AND NEXT SCALE ACTIVITIES

Upgrading biogas to pipeline specification at industrial scale using biocatalyst

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DOE/NETL: This material is based upon work supported by the Department of EnergyNational Energy Technology Laboratory under Award Numbers DE‐FE0004228 and DE‐FE0012862.

Disclaimer: This presentation was prepared as an account of work sponsored by anagency of the United States Government. Neither the United States Government norany agency thereof, nor any of their employees, makes any warranty, express orimplied, or assumes any legal liability or responsibility for the accuracy, completeness,or usefulness of any information, apparatus, product, or process disclosed, orrepresents that completeness, or usefulness of any information, apparatus, product, orprocess disclosed, or represents that its use would not infringe privately ownedrights. Reference herein to any specific commercial product, process, or service bytrade name, trademark, manufacturer, or otherwise does not necessarily constitute orimply its endorsement, recommendation, or favoring by the United States Governmentor any agency thereof. The views and opinions of authors expressed herein do notnecessarily state or reflect those of the United StatesGovernment or any agency.

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ACKNOWLEDGMENTSUS DOE‐NETL Andrew Jones, Project ManagerNovozymes Generous supply of carbonic anhydrasePNNL Charles Freeman, Mark BeardenWorleyParsons Vladimir VaysmanEPIC Systems Pilot Unit fabricationEmerson Process Controls Controls and instrumentation

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