Autothermal Cyclic Reforming and H2 Refueling System · 2004-06-03 · Autothermal Cyclic Reforming...

Autothermal Cyclic Reforming and H2 Refueling System

Ravi Kumar, Court Moorefield, ParagKulkarni, Boris Eiteneer, John Reinker,and Vladimir ZamanskyGE Global ResearchMike ManningPraxair

DOE Project ReviewPhiladelphia, PAMay 2004This presentation does not include any proprietary or confidential information

Autothermal Cyclic Reforming & H2 Refueling2

Outline• Objectives• Project Timeline & Budget• DOE Targets• Accomplishments over last year• Safety Status• Project Plan for Next Year• Summary


Objectives• Overall

> Design a reformer based refueling system that can meet the DOE cost (<$2.50/kg) target

> Fabricate and operate an integrated 60 kg of H2/day reforming and refueling system

• Last Year> Design, fabricate and operate reformer and pressure swing

adsorber pilot-scale sub-systems> Design the prototype reformer and pressure swing adsorber> Design the compression, storage and dispensing system and

collect data on sub-systems


Project Timeline – Major Milestones

Phase I Phase II Phase III01/02 - 12/02 01/03 - 12/04 01/05 - 09/05

• Phase I – Design and Analysis1. Completed conceptual design2. Completed economic analysis

• Phase II – Subsystem Development3. Operated pilot-scale reformer and PSA 4. Completed prototype reformer and PSA design5. Fabrication and shakedown of prototype reformer and PSA

• Phase III – Integrated System Operation6. Integration of ACR with PSA 7. Complete bench-scale catalyst durability testing8. Integration of H2 generator with H2 compressor and dispenser9. Operation of ACR based hydrogen refueling system

21 3 4 5 6 7 8 9


Budget

• Total: $4.8 Million

• Industry: $2.1 Million

• DOE: $2.7 Million

• FY04 Funding: $0.6 Million


Technical Barriers and Targets• Distributed H2 Production from Natural Gas Barriers

> A. Fuel Processor Capital Costs> B. Operation & Maintenance Issues> D. Carbon Dioxide Emissions> E. Control & Safety> Z. Catalysts> AB. H2 Separation & Purification

• Targets

625.02003

7568Efficiency (LHV)1.53.0Cost ($/kg)20102005


Prototype Hydrogen Generating & Dispensing System

H2, CO, CO2,CH4

Recycle Fuel

H2

Com

p.

Storage Tanks

H2

Reformer

Shift Reactor

Pressure

Swing

Adsorber

Vent

DispenserAir

Natural Gas

Water

Praxair

GE Hydro-Pac

Fueling Technologies


Exergy of Reformers for H2 Generation

60%

70%

80%

90%

100%

SMR/ACR ATR

H2

Product (efficiency)

Exergydestruction in Reformer+ HX + Shift

Exergydestruction in Vent + Misc.

H2

Production Exergy

ExergyDestruction in Reformer + HX + Shift

ExergyDestruction in Vent + Misc.

SMR – Steam Methane ReformingACR – Autothermal Cyclic ReformingATR – Conventional Autothermal Reforming


Reformer Choice Depends on Application

75%65%75%Efficiency

Good

Good

Natural Gas, Propane, Diesel Fuel, Biogas

Low

40-50%Conv. ATR

GoodPoorTurndown

GoodPoorSulfur Tolerance

Natural Gas, Propane, Diesel Fuel, Biogas

Natural Gas, Propane

Fuel Flexibility

LowHighCapital Cost

70%70%%H2 from reformer

ACRConv. SMR


Stable Operation of Low-Pressure Pilot-Scale ACR

0

5

10

15

20

25

30

35

40

45

50

0 50 100 150 200 250 300Time (minutes)

CH

4 (%

vol

. dry

)

0

10

20

30

40

50

60

70

80

90

100

H2

and

CO

(% v

ol. d

ry)

CO%

H2%

CH4%


500550600650700750800850900950

1000

0 50 100

150

200

250

300

350

400

450

500

550

600

650

700

Time, minutes

Tem

p, C

Stable Operation of Low-Pressure Pilot-Scale ACR

ACR Reactor Temp


Shift Reactor TestingSpecification: %CO < 1%

0

50

100

150

200

250

0 20 40 60 80 100 120Time, minutes

Tem

pera

ture

, C

0

1

2

3

4

5

CO

, %

Shift Temperature

Shift Outlet CO%


Reformer Testing Accomplishments

• Operated system with about 30 start-stop cycles

• Operated system continuously for up to 30 hours using automated controls several times.

• Demonstrated less than 0.5% CO at exit of shift reactor

• Operated system from 55 kg/day to 15 kg/day (3.5:1 load change)

• Lab scale tests for 2,000 hrs


High Pressure Reformer Reactor: 3-D Stress & Thermal Modeling

3.4Total< 5.0Specification

0.3Bottom2.7Side0.4Top

Heat Loss, kWReformer Zones

> 1,000,000Outer Shell> 1,000Specification

> 90,000Hottest Internal

Cold-Start Cycles to failure

Critical welds


Praxair PSA Pilot Plant Meets Requirements

Design Goals: 60 kg/day, 99.99% H2 purity, 75% recovery

4 bed design> Shortened bed height > Reduced amount of sieve required > Improved recovery

3 bed design> Advanced sieve material> Proprietary 12-step cycle> Lowered feed pressure requirements


• Skid design 75% complete

• Adsorbent - on order

• Logged 300,000 cycles on valves > No detectable leaks using He @ 150

psig

Praxair PSA Prototype Skid Status


~ 100 ppm~ 100 ppm< 2%O2, N2 & Ar< 10 ppm< 10 ppm< 100 ppmHydrocarbons< 1 ppm< 10 ppm< 1 ppmAmmonia< 10 ppb< 50 ppb< 10 ppbSulfur< 5 ppm< 10 ppm< 100 ppmCO2< 1 ppm< 5 ppm< 1 ppmCO

~ 99.9999% dry basis

99.99% dry basis

98% dry basisH2

Status with Future Development

Current StatusDOE TargetsComponent in

the Product

H2 Purity Status


Hydro-Pac Hydraulic H2 Compressor

• Praxair’s LAX project provided an opportunity to gain experience needed for the ACR program

• Measured incoming power and calculated the compressor efficiency during factory run test on helium

67.8%ηadiabatic =


150 psig H2 from Reformer

Stage 1 & 2 Intensifier

Stage 3/ Filling Intensifier

6500 psig H2 to FC vehicle

Dispenser

400-700 psig low P storage bank

1000-6500 psig mid-high P storage bank

Hydraulic fluid reservoir

• Requires 1/3 the amount of storage than cascade dispensing

• Added low pressure storage bank to maximize utilization

• Requires only one “modified” packaged compressor by separating functionality of each intensifier during fill

> Stages 1 & 2 fill low pressure bank

> Stage 3 acts as fill pump

• Small scale testing to begin in 2nd quarter of 2004

Fill Pump Dispensing with Added Low Pressure Bank (Patent Pending)


Stationary Storage

ASME STEEL CYLINDERS

• Plan to use ASME Section VIII, Division 1 Coded seamless steel cylinders

> Designed with a safety factor of 3.0

> Praxair has a perfect safety record when employing these vessels for H2 service

• Work with ASME to develop new rules for composite vessels

> Praxair working with ASME and is actively participating in the H2Steering Committee for storage and transport of H2


Praxair is working with Fueling Technologies on Dispenser

PRIORITY SEQUENCING PANEL

DISPENSER ISLAND

• Safety

• Additions> A vibration switch terminates the fill

operation in the event of vehicle contact and remains locked out until reactivated

> A shear frame assembly and automatic shutoff valves as a safeguard against a more severe vehicular collision

> FTI provided new connections to allow the use of N2 for purging both the enclosure in an LEL shut-down event and for continuously purging the dispenser H2 vent header


Project Safety

REV MAY2002

Likelihood Wt. = 0 Likelihood Wt. = 6 Likelihood Wt. = 3 Likelihood Wt. = 7 Likelihood Wt. = 7

0 PFac 4.20609E-06 PFac 5.76003E-07 PFac 0.000638468 PFac 0.000465474 PFac

F D E C CLikelihood Wt. = 7

0.001108724 PFac

C

% = Likelihood Wt. = 6 Likelihood Wt. = 7 Likelihood Wt. = 3 % = 20 Likelihood Wt. = 3 9 = Severity Wt.

0.001001343 PFac 1.3279E-07 PFac 3.37844E-10 PFac 1.77878E-13 PFac 3.55756E-14 PFac 3.55756E-14 PFac

N/A D C E N/A E E

% = Likelihood Wt. = 3 Likelihood Wt. = 3 Likelihood Wt. = 9 Likelihood Wt. = 7 Likelihood Wt. = 3 % = 20

5.26385E-07 PFac 7.05114E-13 PFac 9.4453E-19 PFac 4.22008E-19 PFac 1.07367E-21 PFac 5.65297E-25 PFac 1.13059E-25 PFac

N/A E E B C E N/A

% = Likelihood Wt. = 7 % = 50 Likelihood Wt. = 3 9 = Severity Wt.

2.63193E-07 PFac 6.69613E-10 PFac 3.34806E-10 PFac 3.34806E-10 PFac Single Unit = N/A C N/A E Entire Fleet =


2.63193E-07 PFac 3.49025E-11 PFac 6.98051E-12 PFac 6.98051E-12 PFac Single Unit = N/A D N/A E Entire Fleet =


5.26385E-07 PFac 1.33923E-09 PFac 2.67845E-10 PFac 2.67845E-10 PFac Single Unit = N/A C N/A E Entire Fleet =

% = Likelihood Wt. = 3 Likelihood Wt. = 7 Likelihood Wt. = 7 Likelihood Wt. = 9 % = 20 Likelihood Wt. = 3 9

5.21112E-05 PFac 6.98051E-11 PFac 1.77598E-13 PFac 4.51843E-16 PFac 7.93491E-14 PFac 1.58698E-14 PFac 1.58698E-14 PFac

N/A E C C B N/A E

% = Likelihood Wt. = 3 Likelihood Wt. = 6 % = 20 Likelihood Wt. = 3 9 = Severity Wt.

5.26385E-07 PFac 7.05114E-13 PFac 6.98051E-11 PFac 1.3961E-11 PFac 1.3961E-11 PFac Single Unit = N/A E D N/A E Entire Fleet =

% = Likelihood Wt. = 3 Likelihood Wt. = 6 % = 20 Likelihood Wt. = 3 9 = Severity Wt.

5.26385E-07 PFac 7.05114E-13 PFac 9.35068E-17 PFac 1.87014E-17 PFac 1.87014E-17 PFac Single Unit = N/A E D N/A E Entire Fleet =


5.26376E-05 PFac 7.05102E-11 PFac 3.52551E-11 PFac 3.52551E-11 PFac Single Unit = N/A E N/A E Entire Fleet =

Safety Score 6.5797E-091.64492E-07

Safety Score 3.49025E-8.72564E-

Node Description 27 Estimated Events

Safety Score 2.60556E-06.5139E-08



Safety Score 4.99882E-081.24971E-06

Node DescriptionIgnition Source

Safety Score 1.30278E-093.25695E-08


1.56213E-06



Safety Score

Ignition SourceInlet Valve Failure

Ignition Source

Air Pressue Drop Valves Closing at Different Times

NG Release

Ignition SourceExplosive Mixture

Residual Gases in System Ignition Source

0.04747665% of failures thatlead to chain X

Vibration During Transport

Valve Position Changing

% of failures thatlead to chain X Purge Failure

NG Accumulation

4.70010562% of failures thatlead to chain X Slow Air Leak


No Flame in Reformer Reactor

4.74758227

0.04747665% of failures thatlead to chain X H2 Fitting/Piping Leak

Ignition Source

Ignition Source

% of failures thatlead to chain X NG Fitting/Piping Leak NG Release

Hydrogen Release


External Impact of NG Line

0.02373833

0.04747665% of failures thatlead to chain X Inlet Valve Failure Air Into Shift &/or

Ox Reactor T Sensor Failure T Increase in Reactor

T/P Buildup in Reactor

Release of H2 and CO

Control Software Failure

Total DefectLikelihood

90.3149288

% of failures thatlead to chain 1 T/P Sensor Failure

Hydrogen Generator (eNPP 01-39.1)Explosion ASR

DesignInadequate

ManufacturingDefect

InstallationDefect

OperationalDefect

MaintenanceDefect

Ignition Source

Control Software Failure Ignition Source

Control Software Failure

Release of H2 and CO

Air Mixing with H2 or NG

Node Description 27

Safety Score 6.24853E-08

and/or and/or and/or and/or

• System Component FMEA’s

• Preliminary Hazard Assessment

• Haz Op (with independent review)

• Accident Scenario Review (performed review on any medium scoring item on Haz Op)


# Task Name

1Low pressure reformer operation

2High pressure reformer designand fabrication

3Catalyst durability testing4PSA design and fabrication5Installation in UCI

6Design of H2 compressor, storageand dispenser

7High pressure ACR reactorshakedown

8High pressure reformer start-upand operation

9Integration with PSA10Integration with PEM fuel cell

11Integration with H2 compressor,storage and dispenser

D J F M A M J J A S O N D J F M A M J J A S O NQ4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q

2004 2005

• Increased Reliability in Startups• Extended Operation

• ASME Codes• Modeling Stress due

to Reformer Cycles

• Catalyst Durability test for 3000 hrs

• Codes & Standards• Safety Reviews

ACR Project Plan for 2004-5


Significant Reviewer Comments• Excellent implementation of economics; Economic analysis should

include reformers from other manufacturers> Working on DOE H2A panel> Supporting DOE on an apples-to-apples comparison of

different reforming technologies• Little innovation outside of GE reformer evident

> Praxair submitted patents on PSA and refueling system recently

> Novel 3-bed and 4-bed designs> Some of the innovation is confidential and will be presented to

DOE • Excellent component developed and test plans; Future plans are

weak> Included a detailed project plan for next year


Summary• Low-pressure pilot-scale ACR operation

> Stabilized for extended periods of time > 30 start-stop cycles

• High pressure prototype reformer design is complete

• Prototype reformer and PSA will be fabricated and operated this year

• Reformer will be integrated with PSA, compressor and storage tanks

• Operation of integrated system in 2005


Ackowledgements

• Department of Energy> Mark Paster, Peter Devlin and Sig Gronich

California Energy Commission> Avtar Bining and Mike Batham

• California Air Resources Board> Steve Church


Questions?

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Autothermal Cyclic Reforming and H2 Refueling System · 2004-06-03 · Autothermal Cyclic Reforming...

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