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Current CO2 Capture Technology Optionsand Advanced R&D Pathway Solutions

Jared Ciferno, Technology ManagerExisting Plants Program

CCESColorado Clean Energy

Solutions

Carbon Capture Rountable and Symposium

October 1, 2009

2

• Only government owned & operated DOE national lab• Dedicated to energy RD&D, domestic energy resources• Fundamental science through technology demonstration• Unique industry–academia–government collaborations

National Energy Technology LaboratoryWhere Energy Challenges Converge and Energy Solutions Emerge

West VirginiaPennsylvaniaOregon

3

Existing Coal

New CoalNatural Gas Petroleum

78% of year 2030 CO2

Emissions from

Existing Coal Plants

Values Calculated from Energy Information Administration’s Annual Energy Outlook ARRA Reference Case Scenario, AEO Does not consider PC with CCS

U.S. Electricity GenerationCO2 Emissions Forecast

Mill

ion

Met

ric T

ons

CO

2/Yea

r

3,000

2,500

2,000

1,500

1,000

500

02005 2010 2015 2020 2025 2030

4

CO2 Capture Experience

1930 19801970196019501940 20001990

Natural Gas SweeteningFood & Chemical Grade CO2

Gasifiers

Coal-Fired Boilers

HydrogenAmmonia

Hydrocarbon RefiningChemical Synthesis

DehydrationGas ProcessingAir Separation

NitrogenEnhanced Oil Recovery

Air SeparationChemical Plants

Carbon DioxideNatural Gas ProcessingEnhanced Oil Recovery

Time

Technology Enablers1. Comparatively small volumes

200 to 4,000 TPD CO2

2. High value products3. Specialized operating

environments

GAS ABSORPTIONPhysical Solvents

GAS ABSORPTIONChemical Solvents

GAS ADSORPTION

GAS SEPARATIONMEMBRANES

5

1. Scale-up• Current PC capture ~200 tons/day

• 550 MWe plant produces 13,000 tons/day

2. Energy Demand• 20% to 30% in power output

3. Cost• Increase Cost of Electricity (COE)

4. Regulatory framework• Transport — pipeline network

• Storage

Deployment Barriers for CO2 Capture on New and Existing Coal Plants Today

6

Fossil Energy CO2 Capture Options

Source: Cost and Performance Baseline for Fossil Energy Power Plants study, Volume 1: Bituminous Coal and Natural Gas to Electricity; NETL, May 2007.

Pulverized Coal (PC)Post-combustion

PC Oxy-combustion

Gasification (IGCC)Pre-combustion

7

Fossil Energy CO2 Capture Solutions

Time to Commercialization

Advanced physical solventsAdvanced chemical solventsAmmoniaCO2 com-pression

Amine solventsPhysical solventsCryogenic oxygen

Chemical loopingOTM boilerBiological processesIonic liquids

Metal organic frameworksEnzymatic membranes

Cos

t Red

uctio

n B

enef

it

PBI membranes Solid sorbentsMembrane systemsITMsBiomass co-firing

Post-combustion (existing, new PC)

Pre-combustion (IGCC)

Oxycombustion (new PC)

CO2 compression (all)

202020152010

OTM – O2 Transport Membrane (PC)ITM – O2 Ion Transport Membrane (PC or IGCC)

8

Supercritical PC Power PlantAmine Scrubbing CO2 Capture

Reference: Pulverized Coal Oxycombustion Power Plants—Volume 1 Bituminous Coal to Electricity, U.S. Department of Energy/National Energy Technology Laboratory, Revision 2 Final Report, August 2008

TPD: Short Ton per DayTPY: Short Ton per Year

*CO2 Capture Process Flow Diagram in Appendix

Amine scrubbing Advantages:• Proven Technology Petroleum

refining, NG purification• Chemical solvent High loadings at low

CO2 partial pressure• Relatively cheap chemical ($2-3/lb)• Tunable to 0 to 90+% capture

Steam: 3500 psig/1110°F/1150°FNOx: LNB, OFA and SCRSOx: Wet limestone FGDPM: Baghouse

9

0

5

10

15

20

25

30

35

40

45

50

Existing New 30% CO2Capture

50% CO2Capture

70% CO2Capture

90% CO2Capture

Net

Effi

cien

cy (%

HH

V)

33%

39%

35%

25 - 35%

31%28%

PC CO2 Capture Efficiency ImpactNew Plant, Bituminous Coal, Amine Scrubbing

Without CO2 Capture With CO2 Capture

CO2 Capture ’s New PC net efficiency by 4 to 12% pts.

CO2 Capture ’s New PC net efficiency by 4 to 12% pts.

References: Pulverized Coal Oxycombustion Power Plants—Volume 1 Bituminous Coal to Electricity, U.S. Department of Energy/National Energy Technology Laboratory, Revision 2 Final Report, August 2008

Integrated Environmental Control Model 2008

10

0

2

4

6

8

10

12

Existing New 30% CO2Capture

50% CO2Capture

70% CO2Capture

90% CO2Capture

Cos

t of E

lect

ricity

(cen

ts/k

wh)

PC CO2 Capture COE ImpactNew Plant, Bituminous Coal, Amine Scrubbing




CO2 Capture ’s Existing COE by ~ 4 — 5X

CO2 Capture ’s Existing COE by ~ 4 — 5X

To Match CA Proposed 1,100 lb/MWhTo Match CA Proposed 1,100 lb/MWh

To Match New NGCC 800 lb/MWh ~ 65% CaptureTo Match New NGCC 800 lb/MWh ~ 65% Capture

TPC ~ $1,600/kW TPC ~ $2,300 - $2,900/kW

11

Advanced Solvent R&D Focus High CO2 loading capacity Minimize regeneration energy Fast reaction kinetics Non-corrosive No solvent degradation Low cost

Advanced CO2 Solvents

Project Types• Ionic liquids• Novel high capacity oligomers• Potassium carbonate/enzymes• CO2 capture additives

Partners (5 Projects): University of Notre Dame, Georgia Tech., Illinois St. Geological Survey, GE Research Corporation, Lawrence Berkeley Nat. Lab

DesignNew compounds with lower heats

of reaction

New compounds with lower heats

of reaction

1,1-di-isopropyl JEFFAMINE

Heat of reaction = -9.4kcal/mol

1,1-di-isopropyl MEA


R RNH2+CO2

0.0

Complex TS1

Carbamiczwitterions

+ RNH2

Complex2 TS2

Carbamate

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC

O

HH

OHH2C

CH2N

H H

HOCH2

H2C

N

OC

O

H

OHH2C

CH2N

H

HH

-2.1 (-2.6) [-2.4]-2.3 (-3.1) [-4.2]

-8.8 (-12.6)[-14.7]

-15.9 (-20.2)[-20.4]

-1.3 (-2.0)[-2.4]

-7.4 (-9.3) [-12.3]

¦¤E (Kcal/mol)

Italcs for JEFFAMINE ( ) for MEA[ ] for Methylamine

The results from the B3LYP/6-31G(d) level using CPCM model

Reaction pathway computed from density functional theory


of reaction


of reaction





R RNH2+CO2

0.0

Complex TS1

Carbamiczwitterions

+ RNH2

Complex2 TS2

Carbamate

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC

O

HH

OHH2C

CH2N

H H

HOCH2

H2C

N

OC

O

H

OHH2C

CH2N

H

HH

-2.1 (-2.6) [-2.4]-2.3 (-3.1) [-4.2]

-8.8 (-12.6)[-14.7]

-15.9 (-20.2)[-20.4]

-1.3 (-2.0)[-2.4]

-7.4 (-9.3) [-12.3]

¦¤E (Kcal/mol)




of reaction


of reaction





R RNH2+CO2

0.0

Complex TS1

Carbamiczwitterions

+ RNH2

Complex2 TS2

Carbamate

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC O

HH

HOCH2

H2C

N

OC

O

HH

OHH2C

CH2N

H H

HOCH2

H2C

N

OC

O

H

OHH2C

CH2N

H

HH

-2.1 (-2.6) [-2.4]-2.3 (-3.1) [-4.2]

-8.8 (-12.6)[-14.7]

-15.9 (-20.2)[-20.4]

-1.3 (-2.0)[-2.4]

-7.4 (-9.3) [-12.3]

¦¤E (Kcal/mol)



Reaction pathway computed from density functional theory

Solvent Screening and Synthesis

Recent chemical formulations show: 50% increase capacity vs. MEA < 48% increase in COE

Laboratory-scale

Source: Novel High Capacity Oligomers for Low Cost CO2 Capture, GE Global Research, GE Energy, University of PittsburghAnnual NETL CO2 Capture Technology for Existing Plants R&D Meeting, March 24-26, 2009

12

Advanced Sorbent R&D Focus • High CO2 loading capacity• Minimize regeneration energy• Fast reaction kinetics• Durable

- Thermally & chemically stable• Gas/solid systems

- Low pressure drop, heat management

Solid CO2 Sorbents

Partners (6 Projects): RTI, UOP, University of Akron, ADA, SRI, TDA

Project Types• Sorbent systems development• Carbonates• Metal organic frameworks• Metal zeolites

Advantages• Low regeneration energy (no water,

low heat capacity, low heat of reaction)

• High equilibrium capacity—high surface area

• Fast kinetics

Challenges• System design

- Pressure drop- Heat integration- Solid transport

• Durability (attrition, chemical stability)

Laboratory-scale

13

Advanced Membrane R&D Focus• High CO2/N2 selectivity & permeability• Durability

- Chemically (SO2), thermally- Physically

• Membrane systems - Process design critical

• Low cost - Capital and energy penalty

CO2 Membranes

Partners: MTR, RTI

Advantages• Simple operation; no chemical reactions, no

moving parts

• Tolerance to high levels of wet acid gases

• Compact and modular with a small footprint

• Relatively low energy use; no additional water used (recovers water from flue gas)

Challenges• Low flue gas CO2 partial pressure

• Particulate matter and potential impact on membrane life

• Cost reduction and device scale-up

• Power plant integration (e.g. sweep gas)

10

20

30

40

50

60

100 1,000 10,000

CO2/N2selectivity

CO2 permeance (gpu)

PolarisTM

Target area identified from

design calculations

Commercial CA membranes

1 TPD CO2 , 6 month testLaboratory to Pilot-scale

14

Pulverized Coal Oxy-combustion

Coal + O2 CO2 + H2OCoal + O2 CO2 + H2O


PC Oxy-combustion Advantages:• 1st generation plants with existing cryogenic ASU cost

competitive with conventional scrubbing• Plant vs. unit operation—multiple cost reduction

opportunities• Co-sequestration options• Applicable to new and existing PC power plants

15

Pulverized Coal Oxy-combustionAdvanced Oxy-combustion R&D Focus• New oxyfuel boilers

- Advanced materials and burners- Corrosion

• Retrofit existing air boilers- Air leakage, heat transfer, corrosion - Process control

• Low-cost oxygen • CO2 purification • Co-capture (CO2 + SOx, NOx, O2)

Challenges• Existing cryogenic ASUs are capital and energy

intensive

• Excess O2 and inerts (N2, Ar) CO2 purification cost

• Existing boiler air infiltration

• Corrosion and process control

Partners (11 projects): Praxair, Air Products, Jupiter, Alstom, B&W, Foster Wheeler, REI, SRI

0

10

20

30

40

50

60

70

Perc

ent I

ncre

ase

in C

OE

Trans., Stor., & Monit.Compression CapitalASU CapitalCompression PowerASU Power

Parasitic Power COE by 37%

Capital Cost COE by 29%

Laboratory to 5 MWe Pilot-scaleNo-capture base = 6.4 cents/kWh

16

Chemical Looping Combustion

Key Challenges• Solids transport• Heat Integration

Key Partners (2 projects): Alstom Power (Limestone Based), Ohio State (Metal Oxide)

Status2010 Alstom Pilot test (1 MWe) 1000 lb/hr coal flow 1st Integrated operation 1st Autothermal Operation

Red

Ox

Me

Air

Fuel CO2 + H2O

MeO

N2 + O2

Steam

Fuel Reactor (Reducer)

Air Reactor (Oxidizer)Oxy-Firing without Oxygen Plant

Solid Oxygen Carrier circulates between Oxidizer and Reducer

Oxygen Carrier: Carries Oxygen, Heat and Fuel Energy

Carrier picks up O2 in the Oxidizer, leaves N2 behind

Carrier Burns the Fuel in the Reducer

Heat produces Steam for Power

17

Perc

ent I

ncre

ase

in C

OE

ADVANCEDUltra-Supercritical

Cryogenic ASU

ADVANCEDAdv. Boiler

O2 MembraneAdv. Materials

Co-SequestrationUltra-Supercritical

ADVANCEDChemical Looping or

Ultra-SupercriticalAdv. Boiler

Adv. MaterialsCo-Sequestration

O2 Membrane

Supercritical OxyfuelCryogenic ASU

AmineScrubbing

Reference: Pulverized Coal Oxycombustion power Plants, U.S. Department of Energy/National Energy Technology Laboratory, Final Report, August 2008

PC Oxy-combustion Pathway

2009 2015 2017 2019 2020-2025

Steam Conditions (psig/oF/oF)Supercritical: 3,500/1,110/1,150 Ultra-supercritical: 4,000/1,350/1,400Note: As of 2009, most advanced cycles are in Japan . Example (3,685/1,120/1,115)

18

IGCC Power PlantWith Pre-combustion SelexolTM CO2 Scrubbing

IGCC CO2 Capture Advantages:1. High PCO22. Low Volume Syngas Stream

SelexolTM CO2 Capture Advantages:1. Physical Liquid Sorbent2. Highly selective for H2S and CO23. CO2 is produced at “some” pressure4. 30+ years of commercial operation (55

worldwide plants)TPD: Short Ton per DayTPY: Short Ton per Year (at 80% Capacity Factor)

1See Appendix for further design conditions: Coal type, Plant Location,Financial Criteria, etc.

References: Cost and Performance Baseline for Fossil Energy Power Plants--Volume 1 Bituminous Coal to Electricity, U.S. Department of Energy/National Energy Technology Laboratory, Final Report, May 2007

19

0

5

10

15

20

25

30

35

40

45

50

Existing PC New IGCC 40% CO2Capture

60% CO2Capture

70% CO2Capture

90% CO2Capture

Net

Effi

cien

cy (%

HH

V)

35%

39%

36%25 - 35%

34%32%

IGCC CO2 Capture Efficiency ImpactNew Plant, Bituminous Coal, Selexol Scrubbing


CO2 Capture ’s New IGCC net efficiency by 3 to 8% pts.CO2 Capture ’s New IGCC

net efficiency by 3 to 8% pts.


Evaluation of Alternate Water Gas Shift Configurations for IGCC Systems, Draft Internal Report,, December 2007

20

0

2

4

6

8

10

12

Existing PC New IGCC 40% CO2Capture

60% CO2Capture

70% CO2Capture

90% CO2Capture

Cos

t of E

lect

ricity

(cen

ts/k

wh)

IGCC CO2 Capture COE ImpactNew Plant, Bituminous Coal, Selexol Scrubbing

Without CO2 Capture

New IGCC with CO2 Capture ’s Existing PC COE by ~ 5X New IGCC with CO2 Capture ’s Existing PC COE by ~ 5X

To Match CA Proposed 1,100 lb/MWhTo Match CA Proposed 1,100 lb/MWh

To Match New NGCC 800 lb/MWh To Match New NGCC 800 lb/MWh


Evaluation of Alternate Water Gas Shift Configurations for IGCC Systems, Draft Internal Report,, December 2007

TPC ~ $1,900/kW TPC ~ $2,300 – $2,800/kW

With CO2 Capture

21

IGCC Pre-combustion CO2 Capture Technologies

IGCC CO2 Capture Advantages:1. High pressure gas stream (High PCO2)2. Low Volume Syngas Stream

CO2 Capture Challenges:1. Integrated power cycles—system

complexity2. Additional water-gas-shift process

10 new projects in 2009• H2/CO2 Membranes

• Solid Sorbents• Advanced Solvents

10 new projects in 2009• H2/CO2 Membranes

• Solid Sorbents• Advanced Solvents

22

Recent Meeting Presentations

http://www.netl.doe.gov/publications/index.html

23

NETL website:www.netl.doe.gov

Annual CO2 Capture Meeting

Jared P. CifernoTechnology Manager, Innovation for Existing PlantsNational Energy Technology LaboratoryU. S. Department of Energy(Tel) 412 [email protected]

Office of Fossil Energy website:ww.fe.doe.gov

For More Information About the NETL Existing Plants Program

Reference Shelf

24

CO2 Capture Goals

By 2020, have available for commercial deployment, technologies that achieve:

90% CO2 capture

< 35% increase in COE for PC, < 10% for IGCC

*Cost of Electricity includes 50 mile pipeline transport and saline formation storage, 100 years of monitoring

Availability analysis of post-combustion carbon capture systems: minimum work input, McGlashan, N.R., Marquis, A.J., Mechanical Engineering Science, Proc. ImechE Vol. 221 Part C, 2007Existing Plants, Emissions & Capture Program—Setting Program Goals, U.S. DOE/National Energy Technology Laboratory, Final Report, April 2009

Set by Systems Analyses Evaluated by Systems Analyses

25

RD&D Timeline to Commercial Deployment

20102008 20162012 2020 2024

Pilot-Scale Field Testing0.5 — 5 MWe

Large-Scale Field Testing5 — 25 MWe

CommercialDeployment

Laboratory-Bench Scale R&D

Large Demonstrations (CCPI) 100+ MWe

*Solvents

*O2 Membrane (2011)

*CO2 Membrane (2012)

*O2 Membrane (2016)*CLC (2016)

*Solvents/Sorbents

- NCCC- Utility sites

26

CO2 Capture from New Coal Plants

2007 “NETL Baseline Study”• Bituminous Coal• ~550 MW net• Subcritical, Supercritical PC• 3 IGCC Types• Selexol and Amine CO2 Capture

2007

2008 “NETL Oxyfuel Study”• Bituminous Coal• 577 MW gross• Supercritical, Ultra-Supercritical P• Cryogenic and Membrane ASU• CO2 Purification Analysis

2008


Source: Pulverized Coal Oxycombustion Power Plants—Volume 1 Bituminous Coal to Electricity, U.S. Department of Energy/National Energy Technology Laboratory, Revision 2 Final Report, August 2008

27

http://www.netl.doe.gov/technologies/carbon_seq/Resources/Analysis/

CO2 Capture from Existing PC Plants

Carbon Dioxide Capture from Existing Coal-Fired Power Plants, U.S. Department of Energy-National Energy Technology Laboratory, Revised Final Report, November 2007

• AEP Plant, Conesville Ohio• Bituminous Coal• 30 Yr. old subcritical PC Plant• 463 MW gross• ESP and Wet Lime FGD• 30, 50, 70 and 90% Capture

2007

• Jim Bridger, Sweetwater Wy• Subcritical PC on PRB coal• 6,700 ft elevation• 577 MW gross• ESP and Wet Soda Ash FGD• 62% and 90% CO2 Capture

2008

28

CO2 Capture Process

29

0

10

20

30

40

50

60

70

80

90Pe

rcen

t Inc

reas

e in

CO

E

Trans., Stor., & Monit.Compression CapitalCapture CapitalCapture OperatingCapture SteamCapture Aux. PowerCompression power

13%

11%

28%

7%

20%

5%2%


Operating Cost COE by 7%


*No Capture Base = 64 mills/kWh*90% CO2 Capture*Compression to 2,200 Psia*50 Mile Pipeline + Saline Formation Storage + 100 Years Monitoring


CO2 Capture Cost of Electricity ImpactNew Plant, Bituminous Coal, Amine Scrubbing

30

CO2 Capture Cost of Electricity ImpactNew Plant, Bituminous Coal, Oxy-combustion


0

10

20

30

40

50

60

70Pe

rcen

t Inc

reas

e in

CO

E

Trans., Stor., & Monit.Compression CapitalASU CapitalCompression PowerASU Power

24%

13%

20%

5%

4%



*No-capture Base = 64 mills/kWh*90% CO2 Capture*Compression to 2,200 Psia*50 Mile Pipeline + Saline Formation Storage + 100 Years Monitoring

31

0

5

10

15

20

25

30

35

40

45

50

Existing New MEA Capture Oxycombustion

Net

Effi

cien

cy (%

HH

V) 39% 25 - 35%

28% 29%

PC Oxycombustion Efficiency ImpactNew Plant, Bituminous Coal

Without CO2 Capture With 90% CO2 Capture



TPC ~ $1,600/kW TPC ~ $2,600 - $2,900/kW

32

0

2

4

6

8

10

12

Existing New MEA Capture Oxycombustion

Cos

t of E

lect

ricity

(cen

ts/k

wh)

PC Oxycombustion COE ImpactNew Plant, Bituminous Coal

Without CO2 Capture With 90% CO2 Capture



33

Oxy-Combustion Pilot with CO2 Purification

Alstom Power

Flue GasAir Products

CO2 Purification Slip-Stream Test:• 2-stage compression/purification • Removes SOx, NOx, O2, & Inerts

34

Chemical Looping Combustion

AshCoolers (6)

SolidsHeater

SealpotControlValves (2)

2-StageCyclones (2)

SprayCoolers &Filters (5)

ReducerOxidizer

ProductGasBurner

Challenges• Solids transport• Heat Integration

Key Partners (2 projects): Alstom Power (Limestone Based), Ohio State (Metal Oxide)

Cold Flow Modeling Completed

Kinetic Rates ExceedDesign Requirements

2010 Alstom Pilot test (1 MWe) 1000 lb/hr coal flow 1st Integrated operation 1st Autothermal Operation

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