hydrogen r&d at ineel - stanford universityjoseph c. perkowski, ph.d. 208-526-5232 april 27,...

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Idaho National Engineering and Environmental Laboratory

HYDROGEN R&D AT INEELOverview

Joseph C. Perkowski, Ph.D.

208-526-5232

April 27, 2004


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Long-Term Vision: “The Hydrogen Model Community”• A “Hydrogen City” or “Hydrogen Corridor” • INEEL, SE Idaho or other venue• Emphasis on engineering validation• Variations

– Treasure Valley Clean Air Non-Attainment Support– Hydrogen Yellow Bus for Greater Yellowstone Ecosystem– GHG-free Southern Idaho Corridor

Electrolysis

PrimaryEnergy Sources

Hydrogen Production

Transport Storage Distribution Use

Photo Conversion

or Compression

Electrolysis


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INEEL Hydrogen Initiative Objectives• Achieve a leading position in RD&D of key hydrogen technologies.

– Focus areas:1. Hydrogen production - nuclear energy,2. Hydrogen production - fossil and/or renewable energy,3. Hydrogen infrastructure - bulk hydrogen handling, vehicle fueling

infrastructure, vehicle testing, fuel cell fabrication/testing.• Gain increased stature as a multipurpose laboratory.• Contribute to the nation’s energy security and an improved

environment.


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Nuclear Hydrogen Production Development Plan

Research and DevelopmentEngineering Demonstration50 MW TC5 MW HTE

Lab Scale

Integrated Lab Scale

Pilot Scale5 MW TC0.5 MW HTE

Demonstration

• Thermochemical (TC)• High Temperature Electrolysis (HTE)• Heat Exchangers and BOP• Membrane and Other

2004 2006 2010 2017


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Hydrogen Production Using Nuclear Energy,INEEL Role

• Program integration and management (w/ Sandia)• Integrated laboratory scale tests• Pilot scale tests • Engineering demonstration • Enabling technology research – kinetics/catalysis, materials,

separations, electrolysis

Thermochemical Cycle High Temperature Electrolysis


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Hydrogen Production Using Fossil or Renewable Energy, INEEL Role• Technology Development and Demonstration

– Reformer processes– Modeling – Gasification technology demonstration– Gas cleanup


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Hydrogen Infrastructure/Utilization,INEEL Role• Fueling infrastructure, vehicle testing

• Distributed hydrogen generation– Electrolysis, liquid fuel reforming/cleanup

• Bulk hydrogen separation, delivery, storage • Fuel cell fabrication/demonstrations

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Absorption of CO2 by Aqueous Diethanolamine Solutions in a Vortex Tube Gas-Liquid Contactor and Separator

Participants: INEEL: Daniel S. Wendt,

(208-526-3996, [email protected])Michael G. Mc Kellar(208-526-1346, [email protected])Anna K. PodgorneyDouglas E. StaceyTerry D. Turner

ConocoPhillips Canada:Kevin T. Raterman

May 6, 2003

Supported by U.S. DOE (DESupported by U.S. DOE (DE--AC07AC07--99ID13727)99ID13727)


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Project Objectives:

• Low capital cost due to compact, simple design• High CO2 capture efficiency

– high efficiency mass transfer– reduced solvent regeneration requirements

• Operationally flexible– turn-down & scale-up with parallel design– easily accommodates variable flow rates and gas

compositions – low maintenance/portable configuration

• Works equally well for physical / chemical absorbents


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Jet type absorbers highly efficientReactor Type kl a ( s-1 x 100)

Packed tower 7

Sieve plate 40

Venturi reactor 25

Bubble column 24

Impinging jet 122

(Herskowits et. al.)

High Shear Jet Absorber

• highly turbulent... large interfacialarea for mass transfer

• multiple jets… impingement zone creates secondary drop breakup / greater area for mass transfer


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High Efficiency Absorption…. acid gas separation

• Co-inject chemical or physical absorbent–– COCO22 + 2R+ 2R22NH NH ↔ RR22NCOONCOO-- + R+ R22NHNH22

++

–– RR22NCOONCOO-- + H+ H22O O ↔ RR22NH + HCONH + HCO33--

–– R designates R designates ––CC22HH44--OHOH• Mass transfer rate ~ f(interfacial area, film thickness)• Vortex tube

– high differential gas-liquid acceleration - small drops– high turbulence - small film thickness

• GOAL … achieve near equilibrium acid gas loading


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Vortex Tube with Liquid Separator

Lorey, et. al., 1998

Cool Gas Outlet8 atm2 °C

Gas Inlet12.6 atm9 °C

Hot Gas Outlet8.6 atm7 °C

Liquid Outlet

J-T Temperature = 5 °C

•Joule-Thomson expansion•near sonic to supersonic velocity


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Scaled Contactor Process-wellhead (~Mscfd) to full gas plant (~MMscfd)-distributed engine (~Mscfd) to centralized power plant (~MMscfd)

Flash

Feed CO2 MixCO2

CO2

StripperAbsorbent

Clean Gas

Parallel Vortex Contactors

(Heat Regeneration if needed)Simple Process Schematic


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Vortex Contactor

Separator TubeSeparator TubeNozzleNozzle

Boroscope / Throttle

Vortex ContactorVortex Contactor

Gas Exit

Liquid inlet

Gas InletLiquid Exit


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Contactor Prototype

60 SLPM @ 100 psia inlet


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Gas - Liquid Loading Tests

• Achieve >95% gas-liquid separation for stoichiometric loading of a 15% volume CO2mixture

• Design parameters– vortex inlet– tube design

• tapered & slotted• stepped with holes

– tube length


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Stepped tube design exceeds gas/liquid separation target

0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000

Inlet Liquid Flow Rate (cm3/minute)

Gas

/Liq

uid

Sepa

ratio

n Ef

ficie

ncy

(%)

0

5

10

15

20

25

30

35

40

45

Liqu

id/G

as R

atio

(mas

s ba

sis)

Separation EfficiencyLiquid/Gas Ratio

Inlet Pressure @ 100 psia


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Stepped tube design exceeds gas/liquid separation target

0

100

200

300

400

500

600

700

800

0 200 400 600 800 1000Inlet Liquid Flow Rate (cm3/minute)

Liqu

id O

utle

t Flo

w (c

m3 /m

in)

0

5

10

15

20

25

30

35

40

45

Liqu

id/G

as R

atio

(mas

s ba

sis)

liquid sidegas sideL/G

Inlet Pressure @ 100 psia


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CO2/DEA Baseline Test Apparatus

CO2supply

N2supply

Reg Reg

CO2 FlowController

N2 FlowController

P

T

T P

GasChromato-

graph

P

P

Flowmeter

Liquid

T

Exit HighFlow

Exit LowFlow

TescomCheck Valve

Tescom

Liquid Pump

LiquidCollect-

ionVessel

LiquidCoalescer

VacuumPump

Hood

Atmosphere

Atmosphere

Vortex Tube

Air InletPress.

Air InletTemp.

Hot AirOutletTemp.

Hot ExitPress.

LiquidOutletTemp

LiquidInlet

Press.

ExitPress.


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CO2/DEA Baseline Testing Operation

• Operating Parameters– 100-500 cm3/min liquid flow rate– 15-50 wt% liquid DEA composition– 80-200 psig inlet gas pressure– 5-15 mol% inlet gas CO2 composition– 25-75 slpm inlet gas flow rate (dependent variable)

• Solvent loading and CO2 capture efficiency unsatisfactory in baseline testing

• Diagnostic testing indicated increased residence time required –process modifications necessary


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Process Modifications

• Modifications to process hardware– increase gas-liquid contact time– capacity to adjust the gas-liquid contactor geometric configuration– maintain ability to control the inlet gas pressure and CO2 : DEA

feed stream mole ratio• Modifications to process operating parameters

– 75-350 cm3/min liquid flow rate– 30 wt% liquid DEA composition– 70 slpm inlet gas flow rate– 10 mol% inlet gas CO2 composition– 170-250 psig inlet gas pressure (dependent variable)


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Baseline and Modified Process Configurations

CO2supply

N2supply

Reg Reg

CO2 FlowController

N2 FlowController

P

T

T P

GasChromato-

graph

P

P

Flowmeter

LiquidSupply

T

Exit HighFlow

Exit LowFlow

Check Valve

Liquid Pump

LiquidCollect-

ionVessel

LiquidCoalescer

VacuumPump

Hood

Atmosphere

Atmosphere

Air InletPress.

Air InletTemp.

Hot AirOutletTemp.

Hot ExitPress.

LiquidOutletTemp

LiquidInlet

Press.

ExitPress.

Contactor

TescomBack Press.Regulator

TescomBack Press.Regulator

ModifiedContactor/Separator

CO2supply

N2supply

Reg Reg

CO2 FlowController

N2 FlowController

P

T

T P

GasChromato-

graph

P

P

Flowmeter

Liquid

T

Exit HighFlow

Exit LowFlow

TescomCheck Valve

Tescom

Liquid Pump

LiquidCollect-

ionVessel

LiquidCoalescer

VacuumPump

Hood

Atmosphere

Atmosphere

Vortex Tube

Air InletPress.

Air InletTemp.

Hot AirOutletTemp.

Hot ExitPress.

LiquidOutletTemp

LiquidInlet

Press.

ExitPress.


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Inlet gas pressure as a function of liquid flow rate

0

50

100

150

200

250

300

0 50 100 150 200 250 300 350


Inle

t Gas

Pre

ssur

e (p

sia)

0

50

100

150

200

250

300

0 50 100 150 200 250 300 350


Inle

t Gas

Pre

ssur

e (p

sia)

No Nozzle Fouling Nozzle Fouling Present

Fouling is caused by deposits accumulating in the vortex tube nozzles


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CO2 capture efficiency as function of liquid flow rate

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 50 100 150 200 250 300 350 400 450 500 550 600


CO

2 Cap

ture

Eff

icie

ncy

(%)

Mo dified Config urat ion 1Mo dified Config urat ion 2

Mo dified Config urat ion 3Mo dified Config urat ion 4Mo dified Config urat ion 5

Mo dified Config urat ion 6Mo dified Config urat ion 7Mo dified Config urat ion 8

Mo dified Config urat ion 9Mo dified Config urat ion 10Mo dified Config urat ion 11Mo dified Config urat ion 12

30 wt% DEA, 10 % CO2, 90 p s ig15wt% DEA, 10 % CO2, 90 p s ig30 wt% DEA, 10 % CO2, MAX ps ig

50wt% DEA, 10% CO2, 10 0 ps ig


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CO2 capture efficiency as function of liquid flow rate (no fouling)

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 50 100 150 200 250 300 350 400 450 500 550 600


CO

2 Cap

ture

Eff

icie

ncy

(%)

Modified Configurat ion 1Modified Configurat ion 2Modified Configurat ion 9Modified Configurat ion 10Modified Configurat ion 11Modified Configurat ion 12


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CO2 capture efficiency as function of liquid flow rate (fouling present)

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 50 100 150 200 250 300 350 400 450 500 550 600


CO

2 Cap

ture

Eff

icie

ncy

(%)

Modified Co nfig uration 3Mod ified Co nfig uration 4Mod ified Co nfig uration 5Mod ified Co nfig uration 6Mod ified Co nfig uration 7Mod ified Co nfig uration 8


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Solvent loading as function of liquid flow rate

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0 50 100 150 200 250 300 350 400 450 500 550 600


Solv

ent L

oadi

ng [m

ole

CO

2/mol

e D

EA] Modifie d Configura t ion 1

Modif ie d Configura t ion 2











30wt % DEA, 10% CO2, 90 psig

15wt % DEA, 10% CO2, 90 psig

30wt % DEA, 10% CO2, MAX psig

50wt % DEA, 10% CO2, 100 psig


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Solvent loading as function of liquid flow rate (no fouling)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0 50 100 150 200 250 300 350 400 450 500 550 600


Solv

ent L

oadi

ng [m

ole

CO

2/mol

e D

EA]

Modified Co nfigurat ion 1Modified Co nfigurat ion 2Modified Co nfigurat ion 9Modified Co nfigurat ion 10Modified Co nfigurat ion 11Modified Co nfigurat ion 12


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Solvent loading as function of liquid flow rate (fouling present)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0 50 100 150 200 250 300 350 400 450 500 550 600


Solv

ent L

oadi

ng [m

ole

CO

2/mol

e D

EA]

Mo dified Config urat io n 3Mo dified Config urat io n 4Mo dified Config urat io n 5Mo dified Config urat io n 6Mo dified Config urat io n 7Mo dified Config urat io n 8


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Conclusions

• Gas/Liquid separation efficiencies in excess of 95%• Non-optimized vortex tube testing has resulted in

carbon dioxide capture efficiencies of up to 86%• Solvent loading as high as 0.49 moles CO2/mole

DEA


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Future Research/Applications

• Process hardware optimization• Scaled contactor and separator• Additional solvents• Additional CO2 applications• H2S


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References• Herskowits,D.; Herskowits,V.; Stephan, K .; Tamir. A.: Characterization of a two-phase

impinging jet absorber. II. Absorption with chemical reaction of CO2 in NaOH solutions. Chem. Eng. Science 45 (1990) 1281-1287

• Lorey, M., Steinle, J., Thomas, K. 1998. “Industrial Application of Vortex Tube Separation Technology Utilizing the Ranque-Hilsch Effect,” presented at the 1998 SPE European Petroleum Conference, The Hague, Netherlands, October 20-22.

• Chakma, A., Chornet, E., Overend, R. P., and Dawson, W. H., “Absorption of CO2 by Aqueous Diethanolamine (DEA) Solutions in a High Shear Jet Absorber”, The Canadian Journal of Chemical Engineering, Volume 68, August 1990.

• Lee, J. I., Otto, F. D., and Mather, A. E., “Solubility of Carbon Dioxide in Aqueous Diethanolamine Solutions at High Pressures”, Journal of Chemical and Engineering Data, Vol. 17, No. 4, 1972.

hydrogen r&d at ineel - stanford universityjoseph c. perkowski, ph.d. 208-526-5232 april 27,...

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