capture of co2 by the carbozyme permeator library/research/coal/ewr/co2/43084...edi multi-stack...

Eighth Annual Conference on Carbon Capture & Sequestration

May 4 -7, 2009 • Sheraton Station Square • Pittsburgh, Pennsylvania

Eighth Annual Conference on Carbon Capture & Sequestration

Session: Capture/Sorbents (1)

Capture of CO2 by the Carbozyme Permeator

May 4 -7, 2009 • Sheraton Station Square • Pittsburgh, Pennsylvania

Robert M. Cowan, David A. Smith, Haibin Chen, Xiaoqiu Wu, Randall S. Reali, Yla A. Angso, Michael C. Trachtenberg

Carbozyme Inc. / Proprietary Information© Copyright 2009 / All Rights Reserved

CarbozymeSolutions for Affordable Clean Energy™

2Michael C. Trachtenberg, PhDCarbozyme, Inc - CEO, CTO

Capture of CO2 by the Carbozyme Permeator

Eight Annual Conference on Carbon Capture & Sequestration

Robert M. Cowan, David A. Smith, Haibin Chen, Randall S. Reali, Yla A. Angso,

Michael C. Trachtenberg



3

Michael TrachtenbergTechnical Manager / CTO

Ira SiderProgram Manager

Technical managementTechnical reportingOutreachR, D & E

BudgetContracts (Management)Management reportingPlanningWeekly reports

Ena

blin

gD

emon

stra

tion

Flue Gas Pre-Treatment

Enzyme Development / Selection

EDI Test Cell Design, Construction, Testing and Selection

SWHF-CLM Scale-up to Pre-Pilot Size

Pre-Pilot Permeator Skid Scale-up

EDI Multi-Stack Scale-up & Test

Engineering & Economic Analysis

Development of a Commercialization Study

Membrane (Module) Manufacturer

Sca

le-u

pE

valu

atio

n

Com

mer

cial

izat

ion

Participants

Eight Annual Conference onCarbon Capture & Sequestration



4

CO2 Scrubber - Detailed Process Flow

1 atm

Pipeline - 2400 psi

O2 , N2 to Permeator

CooledPhase

Change

1200 psi

Compression Stages

O2 Stripper

cool

heat

Stack

N2

O2 Removal

5

13.8% Coal Combustion3.5% Natural Gas Combustion

61.6% 0.4%

1253.5% 12.6%

32 98.3% 95.1%

Feed Gas

Carbozyme System Solution Carbozyme System Solution

Permeator(Membrane Module)

in Skid format

Pre-Treatment(Polisher)




5

Flue Gas Pretreatment• Last year our presentation focused strongly on identification of pretreatment

needs– Conclusion: the most critical need was for removal of SOX– The flue gas source range is

• 330 to 1,000 ppmv for typical dry and wet scrubbed flue gas and/or low sulfur coals• 2000 to over 5000 ppmv for non-scrubbed high sulfur coals

• The Carbozyme acceptance standard for SOX is 7 ppmv (20 ppmw) to sustain a 3-month lifetime of the liquid membrane solution

EERC Analysis using Integrated Environmental Control Model

SOX in Exhaust of Coal Fired Boilers




6

SOX Scrubbing at EERC• The wet lime slurry scrubber, built at EERC, meets the Carbozyme Acceptance Standard

– EERC CEPS fired on SO2 spiked natural gas to low, moderate, and high levels - 860, 2600 & 3300 ppmv

– Pollution Control System on CEPS = SCR, Fabric Filter, Wet Scrubber 1, Polishing Scrubber (CaCO3slurry)

Target - <7ppmv (20ppmw) - Required Performance Achieved

Lime slurry and ceramic Intalox saddle packing for the polishing

scrubber. Packed tower used due to small scale of the test unit.


Time

1

10

100

1000

10000

11:30 12:00 12:30 13:00 13:30 14:00 14:30

SO

2pp

mv

2600

860

3300

5.03 5.09 4.82

SO2 Out of Combustor

SO2 Out of Scrubber 1

SO2 Out of Polishing ScrubberCZ SOx Acceptance Limit, 7 ppmv

62 56 53.5

SO2 measurement method detection limit, 4 ppmv



7

Rationale

• Catalyst• High temperature• Interfacial localization• Stable• Long-lived• Remove & replace

• Apparatus• Maximize surface/volume• Minimize pressure loss• Avoid foaming• Avoid dead & flood zones

Requirements

•Carrier fluid• Maximize capacity• Minimize corrosiveness

• Energy• Minimize total energy• Minimize use of high value

energy - plant derating• Maximize plant independence

• Water• Minimize usage• Maximize recycle




8Technical Merit

Hybrid design achieves benefits of membranes and chemical facilitation

Facilitated Absorption Design Options

<1atm

Chemically Facilitated Absorption CO2 Capture Method OptionsChemistry Description Intermediate Mass Transfer Surface

Area

(m2/m3)

Operation Energy Cost Benefit Format

Interfacial catalyst + Bulk ionic carrier

Liquid Membrane w/ Immobilized

Catalyst

CarbonatesLiquid membrane with immobilized catalyst - HFCLM

600 - 3000 Continuous Vacuum Swing (VSA)Vacuum; CO2

recovered at <1atm

Minimal pumping;

single vessel

Liquid Membrane

Immobilized catalyst + Bulk ionic carrier

Immobilized Catalyst / Bulk Fluid Desorber

Carbonates Absorber/Stripper Tower 300 ContinuousTemperature Swing

(TSA)Low value

heatCO2 recovered

at >1atm

Dissolved catalyst + Immobilized buffer / ionic carrier

Bulk fluid w/ Ion Exchange

beadsCarbonates Absorber/Stripper Tower Swing-bed

Temperature Swing (TSA)

Low value heat

CO2 recovered at >1atm

Dissolved catalyst + Bulk ionic carrier

Modern Bulk Fluid - Mixed

Amines

Carbonates or carbamates

Absorber/Stripper Tower 100 - 250 ContinuousTemperature Swing

(TSA)High value

heatCO2 recovered

at >1atm

Dissolved reactant

Bulk Fluid -Amines / Ammonia

Carbamates or carbonates

Absorber/Stripper Tower 100 - 250 ContinuousTemperature Swing

(TSA)High value

heatCO2 recovered

at >1atm

Interfacial reactant

Solid Sorbent -Carbonates or

AminesCarbonates

Liquid film "solid" bead or immobilized sorbent - beads, fibers or sheets in the gas stream

100 - 600Swing-bed or Continuous

Temperature Swing (TSA)

Pressure (Vacuum) Swing (P/VSA)

Humidity Swing (HSA)

Solids handling;

Vacuum; CO2

recovered at Minimal liquid Film

Tow

er

Enzy

me

Am

ine



9

CO2 = 15%

CO2 = 1.5%

CLM

Rich

CO2

CA CA

Flue Gas

Stack Gas

Vacuum

DIC

CA = Carbonic Anhydrase

N2

CO2

O2 N2O2

CO2

CO2 = 95%

CO2 = 0%

FEED

RETENTATE SWEEP

PERMEATE

H2OvapDIC = Dissolved Inorganic Carbon

Selective Separation through a Liquid Membrane

Fundamental Permeator Design

CO2(g) CO2(d)

H2O H2OH+

HCO3-

2 H+

CO3=CA

Rate Limiting




10

Enzyme Chemistry

Water is a solvent and a reactant

CA splits H2O to provide an OH- reaction center = fast absorption

CA also catalyzes the reverse reaction = fast desorption

Permeate gas




11

CA vs. Amine – Rate vs. Energy

CA - the most efficient, lowest energy catalyst




12

Enzyme Stability & Immobilization

Immobilized enzyme is stable but easily managedImmobilized enzyme is stable but easily managed


Immobilized Enzyme Removal and Replacement

0

20

40

60

80

100

Original Remove Replace%

of

orig

inal

act

ivity

Stability of Immobilized Enzyme Activity

0

20

40

60

80

100

0 15 30 45 60 75 90Time, days

0

50

100

1 2 3 4 5Measurement on Day 1

total of 22 sequential measurements



13

Enzyme Performance Verification

membrane

feedflowpath

CLMspacer

permeateflow path

membrane

Very Small Permeator Small HF ModuleUsed to:- Test and select enzymes- Optimize CLM chemistry- Test immobilized enzyme

Used to test: (0.033 m2)- in-situ immobilization procedure- immobilized enzyme

Flat sheet & hollow fiber immobilized enzyme test bedsFlat sheet & hollow fiber immobilized enzyme test beds




14

Small Module Immobilization Test

InIn--situ immobilization in module works and immobilization is stablesitu immobilization in module works and immobilization is stable

>150 module volumes of CLM buffer were flushed through without loss of activity

Test of Immobilized Enzyme

Gas to Liquid Flow Rate (accm/(mL/min))

CO

2Fl

ux

(mol/

m2-s

)

No EnzymeImmobilized Enzyme

same gasflow rate

same liquid flow rate

Immobilization Procedure Works- this data consistent with stabilityfor the full duration of testing(42 hours)

At time = 0 to 2 hours, 87% CO2 removal(product gas contains 2% CO2)

At time = 26 to 48 hours, 92% CO2

removal (product gas contains 1.3% CO2)

Feed Gas = 15.4% CO2




15

Spiral Wound Permeator

Spacer material providescontrolled thickness for liquid membrane “contained” between the feed/retentate and permeate fibers

Spacer materialFeed/retentate fibersPermeate fibers

Fabrication support




16

Permeator Modifications / Scale-up

0.5 m2 SWHF-CLM Module

0.05 m2 permeator

11 m2 permeator

Small lab test permeatorsBEFORE CURRENT PROJECT

CURRENT STATUS

46 m2 module has been designed

Current Status

2.8*10-4 to 1.9*10-1 m2

Size increase from start: 1,768; 38,797; 162,241



17

Test Results

• TARGET(DOE CCS Goals)– 90% removal of CO2 from a

15% CO2 feed– 95% CO2 dry product gas– Flue gas at design load

– Operating temperature near adiabatic for flue gas

– Permeate pressure as high as possible

• OBSERVED(Shakedown run)– 85.3% removal of CO2 from

a 15.4% CO2 feed – 93.6% CO2 dry product gas – 45.7% of design gas load

– Low operating temperature

– Low permeate pressure




18

System Performance




19

Spacer materialFeed/retentate fibersPermeate fibers

Fabrication support

2-D slice modeled

2-D model slice inside permeator




20

2-D Model Description

CO2 rich

stream

CO2,N2, O2

water vapor

CO2 lean

stream

water vaporgain CO2, N2, O2

lose CO2, N2, O2

x

y

sweep

feed retentate

permeateCLM

Indicates the 2-D slice modeled

CLM

CLM




21

0

2000

4000

6000

8000

10000

12000

14000

16000

Relative location along permeator length

Flue Gas InletCO2 Product Out

Flue Gas OutSweep End

flue gas - no enzyme

flue gas - 1/10th enzyme

CO2 product - 1/10th enzyme

CO2 product - 1/10th enzyme

enzymeimprovesCO2

removalfrom flue gas

enzymeimprovesCO2

productquality

pCO

2 [P

a]

no enzyme

Modeling showing enzyme advantage

83% CO2 removal95% pure CO2 product (dry)

Counter current operation allows for high % removal and high purity permeate

Enzyme Concentration1/10 Design Value


perm

eate

feed

swee

p

rete

ntat

e



22

Initial Performance / Economic Analysis




23

11m2 SWHF-CLM Test Rig

11m2 module




24

Scale-Up to 1t CO2 /day capacity

Next Steps

SWHF-CLM Scale-Up– Assemble 11m2 system

– Test 11m2 system for 2,000hr using spiked natural gas

– Model system to predict and confirm performance of 11m2 system

– Test system for 250hr for each of 3 ranks of coal - lignite, bituminous, sub-bituminous

– Analyze data and publish final report

Enzyme– Fine-tune HF activation approach

to ease commercialization

– Fine-tune immobilization methods for improved enzyme stability, greater retained activity, enhanced remove and replace and in situ

– Demonstrate 90d duration immobilized enzyme at design conditions

Engineering and Economic Analysis– Perform cost/performance analysis of

11m2 system– Perform cost/performance analysis of

multi-module system




25

Future Plans

Pilot Field Test

CarbozymeModular Skids

Natco




26

Acknowledgements

• DOE Project Manager - Jose D Figueroa

• Team Members– Carbozyme - Robert Cowan, David Smith, Xiaoqiu Wu, Haibin

Chen, Randy Reali, Yla Angso, Nikolai Kocherginsky, Burt Waxman

– EERC -Melanie Jensen, Jason Laumb, Bob Jensen– Siemens - Dennis Horazak– Visage Energy - Will Johnson, Daryl-Lynn Robinson, George Hu– SRI - Kevin O’Brien– Argonne National Laboratory - YuPo Lin, Seth Snyder– Kansas State University - Peter Pfromm– ElectroSep - Paul Parisi




27

Acknowledgements

The authors would like to acknowledge José Figueroa

Department of Energy National Energy Technology Laboratory

for his assistance on this project

Project funded by DOE-NETL:DE-FC26-07NT43084

This report 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 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 thereof.




28

The Carbozyme Benefit

Questions?


capture of co2 by the carbozyme permeator library/research/coal/ewr/co2/43084...edi multi-stack...

Documents