New Materials for Hydrogen Pipelines
Barton Smith, Barbara Frame, Cliff Eberle, Larry Anovitz,
James Blencoe and Tim Armstrong
Oak Ridge National Laboratory
Jimmy Mays
University of Tennessee, Knoxville
Hydrogen Pipeline Working Group Meeting
August 30-31, 2005
Augusta, Georgia
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Overview – Barriers and Technical Targets
• Barriers to Hydrogen Delivery
− Existing steel pipelines are subject to hydrogen embrittlement and
are inadequate for widespread H2 distribution.
− Current joining technology (welding) for steel pipelines is major cost
factor and can exacerbate hydrogen embrittlement issues.
− New H2 pipelines will require large capital investments for
materials, installation, and right-of-way costs.
− H2 leakage and permeation pose significant challenges for
designing pipeline equipment, materials, seals, valves and fittings.
− H2 delivery infrastructure will rely heavily on sensors and robust
designs and engineering.
Alternatives to metallic pipelines - pipelines constructed entirely from
polymeric composites and engineered plastics – could enable
reductions in capital costs and provide safer, more reliable H2 delivery.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Overview – Technical Barriers and Targets
2003
Category 2005 2010 2015
Status
Pipelines: Transmission
Total Capital Cost ($M/mile) $1.20 $1.20 $1.00 $0.80
Pipelines: Distribution
Total Capital Cost ($M/mile) $0.30 $0.30 $0.25 $0.20
Pipelines: Transmission and Distribution
Reliability (relative to H2 High
embrittlement concerns and Undefined Undefined Understood (Metrics
integrity) TBD)
H2 Leakage Undefined Undefined <2% <0.5%
From Table 3.2.2, Hydrogen Delivery Targets, in DOE Hydrogen, Fuel Cells & Infrastructure Technologies
Program: Multi-year research, development and demonstration plan, Jan. 21, 2005.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Objectives
• Investigate the use of fiber-reinforced polymer (FRP)
pipeline technology for transmission and distribution of
hydrogen, to achieve reduced installation costs, improved
reliability and safer operation of hydrogen pipelines.
• Develop polymeric nanocomposites with dramatically
reduced hydrogen permeance for use as the barrier/liner in
non-metallic hydrogen pipelines.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
4
Advantages of Continuous FRP Piping
• Anisotropic characteristics of FRP piping provide extraordinary
burst and collapse pressure ratings, increased tensile and
compressive strengths, and increased load carrying capacities.
• No welding and minimal joining - Many miles of continuous
pipeline can be emplaced as a seamless monolith.
• Emplacement requirements should be dramatically less than
those for metal pipe, enabling the pipe to be installed in areas
where right-of-way restrictions are severe.
• Corrosion resistant and damage tolerant.
• Structurally integrated sensors provide real-time structural health
monitoring and could reduce need for pigging.
• Meets or exceeds published and consensus standards for pipeline
in oil and gas applications.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
5
Approach
• Fiber-reinforced polymer (FRP) hydrogen pipeline
− Assess applicability of FRP technology for hydrogen transmission and
distribution pipelines
− Assess methods for achieving technical targets for hydrogen delivery
using FRP pipelines
− Identify potential manufacturing options and joining/repair techniques
− Determine requirements for making technology economically and
practically feasible
Pictures provided courtesy of FiberSpar Corp. Picture provided courtesy of Ameron International.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Approach
• Nanostructured plastics with reduced hydrogen permeance
− Synthesize polymer-layered silicates using organo-modified
montmorillonite (clay) in polyethylene terephthalate (PET)
− Evaluate the hydrogen permeability and mechanical properties of
sample coupons of modified PET
− Optimize permeance of modified PET by adjusting organo-modifier,
clay loading, and extrusion conditions.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Overview – Budget
Task FY 2005
1. Investigate feasibility of using fiber-
reinforced polymer pipeline for H2 $75K
transmission and distribution
2. Develop nanostructured plastic for
use as non-permeable liner in H2 $75K
pipelines
Total $150K
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
8
Interactions and Collaborations
• Existing
− Hydrogen Pipeline Working Group
− University of Tennessee Department of Chemistry -
synthesis of plastics with polymer-layered silicates
• Pending
− Fiber-reinforced polymer pipelines: U.S. manufacturers of
composite piping and storage tanks
− Pipeline infrastructure: Natural gas industries
− Pipeline materials qualification: Savannah River National
Laboratory
− Others
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
9
Technical Accomplishments
• FRP Piping Feasibility – Capital Cost Estimate
− Average hydrogen demand of 0.5 kg H2 per day per capita was
calculated from technical targets and existing transportation data.
However, demand varies diurnally and seasonally, so peak demand of
1.5 times average demand was used as basis for the cost estimate.
− Assume hydrogen generation plant is 200 miles from the population it
serves.
− Spoolable composite piping is available in sizes up to four-inch ID and
with pressure ratings up to 3000 psi. Larger composite pipes were also
considered in this analysis.
− Assume H2 enters pipeline at 1000 psi pressure and the allowable
pressure drop is 300 psi.
− Estimate pipeline sizes required to serve populations of 100,000,
1,000,000 and 10,000,000 people.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Technical Accomplishments
• FRP Piping Feasibility – Capital Cost Estimate
(continued)
Pipeline Requirements for H2 Delivery Assuming
1,000 psi Source Pressure and 300 psi Pressure Drop
Peak H2 4-inch 8-inch 12-inch I.D. for Single
Population Demand Pipelines Pipelines Pipelines Pipeline
Served (kg/h) Req’d Req’d Req’d (inches)
100,000 3,000 5 1 (1) 8
1,000,000 30,000 50 9 3 18
10,000,000 300,000 500 90 30 44
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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Technical Accomplishments
• FRP Piping Feasibility – Capital Cost Estimate
(continued)
− Current capital cost (materials and installation) for 4-inch ID, 1000
PSI-rated FRP piping is $50K to $100K per mile.
− Transmitting H2 to a population of 100,000 would require five 4-inch
ID pipelines, at an approximate capital cost of $250K to $500K per
mile, not including right-of-way costs.
− This estimate is below the DOE 2015 target for hydrogen delivery
($800K per mile).
− However, current fiber-reinforced piping needs liner with acceptably
low hydrogen permeation and needs qualification for high-pressure
H2 service.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
12
Technical Accomplishments
• Preparation and evaluation of PET/clay
nanocomposites
− Synthesized nanocomposites by solution mixing PET and organo-
modified clay in phenol/chloroform solvent
− Prepared PET nanocomposites with clay contents of 5 and 10 wt%
− Modified PET films prepared for analysis and testing by pressing
dried mixtures of PET/clay into thin membranes
− Evaluated nanostructure of films using SAXS and TEM
− Evaluated hydrogen permeability using ORNL hydrogen service
IHPV test facility
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
13
Technical Accomplishments
• Small-angle x-ray scattering (SAXS)
− Intercalation of PET chains
increases interlayer spacing,
shifting peak to lower Q values
− Exfoliation of PET/clay would be
evidenced by broadening of peak
• Transmission electron
microscopy (TEM)
− Images of PET with 5% (left)
and 10% (right) clay contents
− Clay appears as dark lines
− Most clay occurs as
intercalated clusters with only
partial exfoliation
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
14
Technical Accomplishments
• H2 permeation measurements in ORNL IHPV
− Initial modified PET sample exhibited 60%
decrease in diffusion rate coefficient
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
15
Technical Accomplishments
• Preparation and evaluation of sulfonated
PET/clay nanocomposites
− Second formulation of PLS nanocomposites involved partial
sulfonation of PET to obtain a higher degree of exfoliation.
− A white solid powder of PET with 3% sulfonation was produced.
− Nanocomposites were prepared in sulfonated PET (s-PET) by
solution mixing and films were pressed at high temperature and
pressure.
− PET/clay samples with clay contents of 5 and 10 wt % were
prepared for analysis and testing by pressing dried mixtures of
PET/clay into thin membranes
− Evaluated clay dispersion in films using SAXS
− Evaluated hydrogen permeability using ORNL hydrogen service
IHPV test facility
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
16
Technical Accomplishments
• Evaluation of sulfonated PET/clay
nanocomposites
SAXS profiles of
neat PET,
PET/5% clay
and s-PET/5%
clay.
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
17
Technical Accomplishments
• Summary of permeation measurements to date
Sample T (°C) D (×10-4 cm2/s)
PET 15 5.9
PET/10% clay 16 2.3
s-PET 22 18.2
s-PET/5% clay 23 12.2
Kynar (PVF) 24 Similar to PET
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
18
Future Work – Milestones
• FY 2005
− On schedule to complete milestones
• May 2005 - PET-based polymer-layered silicate composite
barrier materials prepared and ready for permeability testing.
• Sep 2005 - Report on FRP pipeline feasibility and
recommendations to be completed.
• Sep 2005 - Assessment of hydrogen permeability in barrier
material coupons to be completed.
• For FY 2006
− Recommendations for sensor integration, manufacturing and
joining technologies
− Further optimization of nanostructured plastic liner
− Bench-scale tests of integrated nanostructured plastic liner and
FRP pipe
OAK RIDGE NATIONAL LABORATORY
U. S. DEPARTMENT OF ENERGY
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