Cec 600 2005 001

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CALIFORNIA
ENERGY
COMMISSION
FAILURE MODES AND EFFECTS
ANALYSIS FOR HYDROGEN
FUELING OPTIONS
November 2004
CEC-600-2005-001
CALIFORNIA
ENERGY
COMMISSION
Prepared By:
TIAX LLC
1601 De Anza Blvd., Suite 100
Cupertino, CA 95014
Contract No. 600-01-095
Prepared For:
Bill Blackburn
Sandra Fromm
Project Managers
Charles Mizutani
Manager
Transportation Technology Office
Rosella Shapiro
Deputy Director
Transportation Energy Division
Robert L. Therkelsen
Executive Director
DISCLAIMER
This report was prepared as the result of work sponsored by the
California Energy Commission. It does not necessarily represent
the views of the Energy Commission, its employees or the State
of California. The Energy Commission, the State of California, its
employees, contractors and subcontractors make no warrant,
express or implied, and assume no legal liability for the
information in this report; nor does any party represent that the
uses of this information will not infringe upon privately owned
rights. This report has not been approved or disapproved by the
California Energy Commission nor has the California Energy
Commission passed upon the accuracy or adequacy of the
information in this report.
i
FAILURE MODES
AND EFFECTS
ANALYSIS FOR
HYDROGEN
FUELING OPTIONS
Technical Consultant
Report
Report to
California Energy Commission
1516 Ninth Street
Sacramento, California 95814-5512
Date: November 2004
Prepared by
TIAX LLC
1601 S. De Anza Blvd., Suite 100
Cupertino, California 95014-5363
Tel 408-517-1550
Fax 408-517-1553
TIAX LLC
Shyam Venkatesh
Stefan Unnasch
St. Croix Research
Charles Powars
IO Mosaic
Henry Ozog
SDV-SCC
J ohn Woody
Technical Consultant Report TR-03-177
TIAX Case D0130
ii
PREFACE
This report was prepared by TIAX LLC for the California Energy Commission as part of
the Energy Commission Contract 600-01-095, Hydrogen Fueling Infrastructure Study. It
is a deliverable required under Task 4, Failure Modes and Effects Analysis. This report
was prepared by TIAX and its subcontractors: St. Croix Research, the University of
California at Davis, Institute of Transportation Studies, SunLine Services Group,
ioMosaic, and SDV-SCC. Bill Blackburn and Sandra Fromm were the Energy
Commission Project Managers. J ennifer Williams provided valuable editing of this
report.
iii
TABLE OF CONTENTS
Preface.............................................................................................................................ii
Abstract ...........................................................................................................................ix
1. Introduction and Background............................................................................. 1-1
1.1 Opportunities for Hydrogen Fueling........................................................ 1-1
1.2 Requirements for Safety Analysis........................................................... 1-1
1.3 Objective................................................................................................. 1-2
1.4 Approach ................................................................................................ 1-4
1.5 Report Organization................................................................................ 1-6
2. Fueling Station Options ..................................................................................... 2-1
2.1 Fueling Station Equipment...................................................................... 2-2
2.1.1 Delivery from Central Hydrogen Plant .................................................... 2-2
2.1.2 On-Site Hydrogen Production................................................................. 2-3
2.1.3 High Pressure Compression................................................................... 2-4
2.1.4 Compressed Gas Storage ...................................................................... 2-4
2.1.5 Vehicle Fueling Dispenser ...................................................................... 2-5
2.2 Fueling Station Design Basis.................................................................. 2-5
2.3 Fueling Station Documentation Failure Modes and Effects
Analysis (FMEA) Perspective ................................................................. 2-6
3. Failure Modes and Effects Analysis................................................................... 3-1
3.1 Liquid Hydrogen Refueling Station FMEA .............................................. 3-5
3.1.1 General Description................................................................................ 3-5
3.1.2 FMEA Results......................................................................................... 3-5
3.2 Electrolyzer Refueling Station FMEA.................................................... 3-15
3.2.1 General Description.............................................................................. 3-15
3.2.2 FMEA Results....................................................................................... 3-15
3.3 Steam Methane Reformer Refueling Station FMEA ............................. 3-24
3.3.2 FMEA Results....................................................................................... 3-25
3.4 Tube Trailer Compressed Hydrogen Refueling Station FMEA.............. 3-34
iv
3.4.2 FMEA Results....................................................................................... 3-34
3.5 CNG Refueling Station FMEA............................................................... 3-42
3.5.2 FMEA Results....................................................................................... 3-43
4. Fueling Station Documentation FMEA Inputs ............................................... 4-1
4.1 Liquid Hydrogen Documentation............................................................. 4-1
4.2 Electrolyzer Documentation.................................................................... 4-9
4.3 Steam Methane Reformer (SMR) Documentation ................................ 4-17
4.3.1 Hydrogen Generation ........................................................................... 4-17
4.4 Tube Trailer Documentation ................................................................. 4-26
4.4.1 Equipment Description.......................................................................... 4-26
4.5 Compressed Natural Gas (CNG) Documentation................................. 4-34
4.5.1 Natural Gas Refueling Station Major Components ............................... 4-34
4.5.2 Refueling Station Nominal Design Basis .............................................. 4-34
5. Comparison of Safety Issues for Hydrogen and Other Fuels ............................ 5-1
5.1 Introduction............................................................................................. 5-1
5.2 Hydrogen Properties............................................................................... 5-2
5.3 Fuel Property Comparisons and Implications ......................................... 5-5
5.3.1 Properties Affecting Leakage.................................................................. 5-5
5.3.2 Buoyancy................................................................................................ 5-5
5.3.3 Flammability Limits and Ignition Energy ................................................. 5-6
5.3.4 Burning Velocity...................................................................................... 5-7
5.3.5 Heating Value ......................................................................................... 5-7
5.3.6 Detectability ............................................................................................ 5-8
5.3.7 Quenching Distance ............................................................................... 5-9
5.3.8 Liquid Hydrogen Properties .................................................................... 5-9
5.4 Hydrogen Compared to Natural Gas .................................................... 5-10
5.5 Hydrogen Leak, Fire, and Explosion Risk Summary............................. 5-10
6. Conclusion......................................................................................................... 6-1
References................................................................................................................. R--1
v
LIST OF TABLES
Table 1-1. FMEA Team............................................................................................ 1-5
Table 1-2. Report Organization and Contents (recommended flow for reading
new to hydrogen-based refueling and safety issues).............................. 1-7
Table 2-1. Fueling Station Options for FMEA Study................................................ 2-1
Table 2-2. Refueling Station Common Design Bases.............................................. 2-6
Table 2-3. Refueling Station Characteristics............................................................ 2-6
Table 3-1. Frequency and Consequence Ratings.................................................... 3-3
Table 3-2. Risk-Binning Matrix................................................................................. 3-4
Table 3-3. Combustion Properties of Hydrogen, Natural Gas and Gasoline
a
.......... 3-4
Table 3-4. Liquid Hydrogen Station FMEA Results.................................................. 3-6
Table 3-5. Risk-Binning Matrix Liquid Hydrogen Delivery, Compressed Gas
Fueling.................................................................................................. 3-13
Table 3-6. Electrolysis Station FMEA Results........................................................ 3-17
Table 3-7. Risk-Binning Matrix Electrolysis Hydrogen Production,
Compressed Gas Fueling..................................................................... 3-23
Table 3-8. SMR Station FMEA Results.................................................................. 3-26
Table 3-9. Risk-Binning Matrix SMR Hydrogen Production, Compressed
Gas Fueling.......................................................................................... 3-32
Table 3-10. Tube Trailer Hydrogen Station FMEA Results...................................... 3-35
Table 3-11. Risk-Binning Matrix Tube Trailer Delivery, Compressed Gas
Fueling.................................................................................................. 3-41
Table 3-12. CNG Station FMEA Results.................................................................. 3-44
Table 3-13. Risk-Binning Matrix CNG, Compressed Gas Fueling........................ 3-48
Table 4-1. Liquid Hydrogen Equipment and Product Specification.......................... 4-4
Table 4-2. Codes and Standards Regarding Compressed and Liquid
Hydrogen Storage................................................................................... 4-7
Table 4-3. Electrolyzer Equipment and Product Specification............................... 4-10
Table 4-4. Codes and Standards Regarding Compressed Hydrogen Storage...... 4-13
Table 4-5. Electrolyzer-Based Refueling Station Operating Procedures................ 4-15
Table 4-6. Electrolyzer-Based Refueling Station Safety Measures........................ 4-16
Table 4-7. SMR/PSA Equipment and Product Specification Summary.................. 4-19
vi
Table 4-9. SMR-Based Refueling Station Operating Procedures .......................... 4-24
Table 4-10. SMR-Based Refueling Station Safety Measures .................................. 4-25
Table 4-11. Tube Trailer and Compressed Hydrogen Equipment and Product
Specification......................................................................................... 4-27
Table 4-13. Tube Trailer Delivery-Based Refueling Station Operating
Procedures ........................................................................................... 4-32
Table 4-14. Tube Trailer Delivery-Based Refueling Station Safety Measures......... 4-33
Table 4-15. CNG Fueling Station Common Design Bases ...................................... 4-34
Table 4-16. Compressed Natural Gas Equipment and Product Specification.......... 4-36
Table 4-17. Codes and Standards Regarding Compressed Natural Gas Storage... 4-39
Table 5-1. Properties of Hydrogen and Other Current and Potential
Automotive Fuels
25
................................................................................. 5-3
Table 5-2. Energy Release Following Ignition of Hypothetical Uniform Fuel-Air
Mixtures in an 85-m
3
Garage.................................................................. 5-8
Table 5-3. Summary Comparison of Key Hydrogen and Natural Gas Safety
Implications........................................................................................... 5-11
Table 5-4. Hydrogen Properties and Characteristics that make it more Prone
or Less Prone to Leaks, Fires, and Explosions Relative to Other
Fuels..................................................................................................... 5-12
vii
LIST OF FIGURES
Figure 1-1. The Safety Analysis Included a Review of Safety Issues for All
Fuels, Analysis of Hydrogen and CNG Fueling Systems, Followed
by FMEA of Hydrogen and CNG Fueling Systems ................................. 1-5
Figure 2-1. Key Components of Hydrogen Refueling Stations.................................. 2-2
Figure 4-1. Pressure versus Enthalpy for Equilibrium Hydrogen, Illustrating Two
Alternative Paths for Dispensing Compressed Hydrogen from
Stored Liquid Hydrogen.......................................................................... 4-2
Figure 4-2. Illustration of Liquid Hydrogen Storage Tank Saturation Pressure
Variation: Pressure Changes for Noted Conditions for Withdrawal of
Liquid, Vapor, or Liquid-vapor Mixture.................................................... 4-3
Figure 4-3. Process Flow Diagram for Liquid Hydrogen Refueling........................... 4-5
Figure 4-4. Piping and Instrumentation Diagram for Liquid Hydrogen Refueling...... 4-6
Figure 4-5. Liquid Hydrogen-Based Refueling Station Site Plan............................... 4-8
Figure 4-6. Electrolyzer-Based Refueling Station Process Flow Diagram............... 4-11
Figure 4-7. Piping and Instrumentation Diagram for Electrolyzer-Based
Refueling............................................................................................... 4-12
Figure 4-8. Electrolyzer-Based Refueling Station Site Plan.................................... 4-14
Figure 4-9. SMR-Based Station Process Flow Diagram......................................... 4-20
Figure 4-10. Piping and Instrumentation Diagram for Steam Methane Reforming-
Based Refueling................................................................................... 4-21
Figure 4-11. SMR-Based Refueling Station Site Plan............................................... 4-23
Figure 4-12. Tube Trailer Delivery-Based Refueling Station Process Flow
Diagram................................................................................................ 4-28
Figure 4-13. Piping and Instrumentation Diagram for Tube Trailer Delivery-
Based Refueling................................................................................... 4-29
Figure 4-14. Compressed Hydrogen Delivery-Based Refueling Station Site Plan.... 4-31
Figure 4-15. Compressed Natural Gas Refueling Station Process Flow Diagram.... 4-37
Figure 4-16. Piping and Instrumentation Diagram for Compressed Natural Gas
Refueling............................................................................................... 4-38
Figure 4-17. Compressed Natural Gas Refueling Station Site Plan.......................... 4-40
Figure 5-1. Hydrogen is Substantially More Buoyant than Air and Other Current
and Potential Automotive Fuels .............................................................. 5-6
ix
ABSTRACT
Hydrogen has generated considerable interest in California and nationwide as a vehicle
fuel to address clean air goals and petroleum dependency issues. The successful
proliferation of hydrogen-fueled vehicles statewide will require expansion of the network
of hydrogen fueling stations. Safe practices in production, storage, distribution, and end-
use of hydrogen are essential for the successful introduction of hydrogen vehicles.
The objective of this report is to develop a safety analysis that will be useful for
stakeholders involved in the development, approval, procurement, and operation of
these stations and the hydrogen vehicles.
Specifically, this report addresses:
Key safety issues related to the design, installation, and operation of four types of
hydrogen fueling stations and a compressed natural gas (CNG) fueling station
(delivered liquid hydrogen, on-site electrolysis, on-site reformation of natural gas,
and delivered compressed hydrogen gas).
Key hydrogen fueling station failure modes typical of selected fueling stations.
Assignment of risk level to failure modes and provides, where necessary and
applicable, recommendations for mitigating the risk level.
Key safety issues associated with the different fueling approaches.
Information on unique properties of hydrogen necessary for a detailed understanding
of the fuel.
A top-level safety analysis was performed using the Failure Modes and Effects Analysis
(FMEA) technique a powerful engineering tool that helps to identify potential problems
that may exist in a product or process before they occur.
Generic designs for the five types of fueling stations presented in this report, as well as
other information available to the FMEA team, provided the basis for the analysis. The
FMEA was performed by a panel with expertise on various aspects of the hydrogen
fueling station, including engineering, construction, operation, and the identification of
potential failure modes. The panel participants also had experience in implementing
design changes to facilitate safety improvements for fueling systems.
The results of the safety analysis are presented in a standard FMEA tabular-format.
While there are differences in each of the five station types that were considered, the
over-arching safety issue is the explosive and flammable properties of hydrogen. Other
safety issues arise from the presence of high-pressure compression and storage
systems and the presence of a cryogenic liquid in the case of liquid hydrogen. The
FMEA team observed that existing designs and installations followed good engineering
x
practices that address safety concerns. However, the team also noted that existing
systems are very few in number and are often demonstration systems.
For the five types of stations, safety risk was classified into high, medium, and low risk
categories using a risk binning technique (the process of categorizing the relative risk of
events by assigning a bin number from a frequency-consequence matrix). The number
of top-level failure modes ranged from 35 to 44 for the four types of hydrogen energy
stations. Twenty-six top-level failure modes were identified for the CNG fueling station;
however, only one failure mode was assigned to the high-risk category. Where
applicable, the report includes recommendations to either prevent the failure mode from
occurring or to lower the overall risk level.
1-1
1. INTRODUCTION AND BACKGROUND
This report is the second volume in a series of five produced by contractors for the
California Energy Commission. Its intent was to examine a variety of issues related to
hydrogen fueling infrastructure. The report provides information on the factors affecting
the safety of hydrogen fueling stations. It includes a review of fuel properties, which
serves as an input to a Failure Modes and Effects Analysis (FMEA) of different
hydrogen fueling systems.
1.1 Opportunities for Hydrogen Fueling
Increased interest in hydrogen as a vehicle fuel may spur construction of more
hydrogen fueling stations in California. These fueling stations may be built as part of
vehicle demonstration programs sponsored by the U.S. Department of Energy (DOE),
South Coast Air Quality Management District, and others, or to meet California Air
Resources Board (ARB) requirements for low or zero emission transit buses or
passenger cars. The ARBs regulations for transit buses require buses purchased in the
future to achieve lower emission levels than todays diesel buses. Some transit
agencies are opting to meet the requirement with hydrogen fuel cell buses (ARB
1999a). Automobile manufacturers may also use hydrogen fuel cell vehicles to meet
some of the ARBs requirements for zero emission vehicles (ARB 1999b).
In April 2004, Governor Schwarzenegger signed Executive Order S-7-04, establishing a
California Hydrogen Highway Network and outlining his vision of expanding the use of
hydrogen for transportation and other sectors. Aimed at installing more than 100
hydrogen fueling stations by 2010, the need for a well grounded understanding of
hydrogen safety issues is greater than ever.
1.2 Requirements for Safety Analysis
Safe practices in the production, storage, distribution, and use of hydrogen are essential
for the successful proliferation of refueling stations for hydrogen vehicles. Insurability of
such stations also hinges on the safe practices adopted. To avoid safety hazards it is
necessary to implement practices that, if adopted early in the development of a fueling
station project, will provide an environment where safety is an integral component. One
such practice is to develop a safety plan that identifies immediate (primary) failure
modes as well as any secondary failure modes that may result from other failures. In
such a plan, every conceivable failure is identified, from catastrophic failures to benign
collateral failures.
Safety plans for fueling stations will be based on Identification of Safety Vulnerabilities,
referred to as ISV. The safety analyses, or ISV, can consist of an FMEA, hazard
analysis (HazOp), or probability risk assessment (fault tree analysis). The three
methodologies are all established industry standards for reliability engineering. The
1-2
purposes are to analyze design components for safety hazards and to demonstrate an
understanding and anticipation of component failures. The most important objective is
the prevention of problems before they occur.
A FMEA identifies significant safety concerns in advance, before the project is fully
implemented. The most important objective of the FMEA is the prevention of problems
through the identification of areas that are prone to failure. If a failure does occur, the
FMEA will contribute to minimizing the effects of that failure.
Prior to performing the ISV, information is compiled for the review team. Pertinent
information includes:
Component specifications and configurations
Component interaction information
Operating procedures
Equipment types
The DOE requires a safety analysis for all of the fueling stations that will be built under
its vehicle and infrastructure demonstration program (DOE 2003a). The requirements
for these analyses are documented by DOE (DOE 2003b). This report could facilitate
the planning process for more detailed site-specific safety analyses for vehicle
demonstration programs.
1.3 Objective
The objective of this report is to develop a safety analysis that will be useful for
stakeholders involved in the development, approval, procurement, or operation of
infrastructure for hydrogen-fueled vehicles. This report covers a range of hydrogen
fueling options and also addresses some safety aspects for other fuels. After reviewing
candidate approaches for this study with stakeholders, the project team and sponsors
agreed that the analysis in this report should be aimed at the potential operators and
permitting authorities of a hydrogen fueling station, rather than at the installers or
technology developers who already have extensive experience with fueling systems.
An FMEA is a method of identifying safety issues (or problems in manufacturing
processes) before they occur. These efforts are often part of the quality system in a
design process. FMEAs typically can be categorized into four types: System, Design,
Process, and Service. The Process FMEA, analyzes the activities and steps involved
with a system. The Design FMEA analyzes equipment, controls, operating procedures,
safety protocols, and other design parameters. The analyses contained in this report
follow the steps from hydrogen supply through dispensing. Specific aspects of fueling
station designs were assumed by the FMEA team, which makes the analysis in this
study a hybrid of a Process and Design FMEA. The potential outcome is a ranked list of
failure modes, a potential list of system functions that could detect failure modes, and a
1-3
list of actions to eliminate failure modes or safety issues. Several references exist that
describe the FMEA process (e.g., Stamatus, McDermott).
A more detailed FMEA based on one specific fueling station design was also
considered in lieu of the format described above. This approach was avoided for several
reasons. First, publishing an FMEA for a specific fueling station requires the
documentation of design details, which raises concerns over the dissemination of
confidential information. Second, publishing an analysis of the safety issues associated
with an existing fueling system might result in unforeseen liability issues. Third, the
project team observed that most FMEAs performed for industry are generated as a tool
to improve the safety of a system or process and are not released to the public. Finally,
a very detailed FMEA would provide an overload of information to most readers, and the
analysis would become obsolete as fueling station designs evolve.
The FMEAs in this study are not intended to serve as a comparison of the safety risks of
different fuel supply options. The FMEA method is intended to identify
recommendations for improving safety and does not provide a quantification of the
relative safety of one fuel supply option compared with others. A numerical
quantification of the risk of injury from one or more types of facilities could be
accomplished with a fault tree analysis. However, such an analysis would require far
more detailed information, including that needed for further site and equipment design,
than is presented in this study.
This report includes an FMEA of fueling stations with four different hydrogen supply
options as well as compressed natural gas (CNG) fueling.
The fueling options included in this report are:
1. Delivery of liquid hydrogen, liquid storage, vaporization, gas compression, gas
storage and dispensing
2. Delivery of electricity, electrolysis, gas compression, storage and dispensing
3. Delivery of natural gas by pipeline, reforming, gas compression, storage and
dispensing
4. Delivery by compressed hydrogen tube trailers, gas compression, storage, and
dispensing
The CNG fueling system includes the following:
5. Delivery of natural gas by pipeline, compression, storage and dispensing
A review of safety issues associated with other fuels is also included to inform decision-
makers of the different risks associated with gaseous and liquid fuels. The issues
associated with fuel properties, flammability ranges, and other safety properties are
discussed for hydrogen, CNG, liquid hydrogen, LPG, methanol, gasoline, and diesel.
1-4
1.4 Approach
The FMEA process typically is applied to a specific design, which is documented by a
complete drawing package. Accurate quantitative results are produced when reliable
statistics are available to characterize the appropriate initiating and contributing failure
events; however, this report is based on a generic design of each type of fueling station
noted above. Specific designs, while available to a limited extent to the FMEA team,
would shift the focus of the report from a broad guideline to a site-specific document.
The failure quantification process for an FMEA based on generic design is less
straightforward, since statistical data for design specific initiating events are unknown
and may have to be approximated. This is also true for early stage conceptual designs,
as in the case of some of the hydrogen fueling stations.
The generic approach presents a top-down high-level FMEA for the four types of
hydrogen refueling stations and the CNG station discussed in this report. This
preliminary approach is suitable when specific components, design, installation, and
operational details have not been chosen. The objective of this approach is to identify
the most likely failure modes that will be applicable to all hydrogen refueling stations. It
identifies and ranks the components and processes with the highest safety risks, the
specific causes and effects of the risks, design approaches and/or operating procedures
to mitigate the risks, and the relationship of the risks to current or recommended codes
and standards. Furthermore, the FMEA for the hydrogen fueling station can also be
used as a qualitative comparison of the risks of different hydrogen fueling options as
compared to natural gas fueling.
Figure 1-1 shows the steps involved in the top-down safety analysis followed in this
report. A generic design in the form of generic process flow diagrams (PFDs), piping &
instrumentation diagrams (P&IDs), operating procedures, site plans, etc., was
completed for each fueling option with enough detail for the FMEA team to perform the
high-level analysis.
The team developed baseline risk scenarios for each fueling system. Section 3 presents
the baseline risk analyses in the form of FMEA worksheets, which were later used by
the analysis team. A facilitated team meeting conducted the FMEA. Table 1-1 shows
the FMEA team members.
1-5
Top-down Fueling System Safety Analysis
Define Fuel Supply
Options
System Analysis Safety Analysis
c
H
2
N
G
Tube Trailer
LH
2
Delivery
NG Steam
Reformer
Electrolyzer
CNG
O
t
h
e
r

F
u
e
l
s
Gasoline
Diesel
LPG
Liquid Hydrogen (LH
2
)
u Fuel properties
u Fuel system
description
u Process flow diagram
u Representative key
features P&ID
u Site Plan
u Fuel properties
u Fuel system
description
u Develop scenarios
u Conduct FMEA
meeting
u Evaluate risks, effects,
and mitigation
measurements
u Identify alternate
configurations
u Identify parameters
that affect safety
Figure 1-1. The safety analysis included a review of safety issues for all fuels,
analysis of hydrogen and CNG fueling systems, followed by FMEA of
hydrogen and CNG fueling systems.
Table 1-1. FMEA Team
Participant Organization
Henry Ozog FMEA facilitator
Shyam Venkatesh
Stefan Unnasch
Charles Powars
Anthony Eggert
J onathan Weinert
Todd Suckow
J ohn Woody
J ohn Williams
ioMosaic
TIAX
TIAX
St. Croix Research
U.C. Davis ITS
U.C. Davis ITS
California Fuel Cell Partnership
SDV-SCC
Sunline Services Group
1-6
During the sit-down FMEA meeting, the team reviewed each of the risk scenarios and
discussed a rating for the likelihood of the safety event occurring, the consequences of
the event, and the potential for safety systems preventing the event from occurring.
Recommendations and mitigation opportunities were identified where the FMEA team
observed opportunities to address safety risks.
1.5 Report Organization
Table 1-2 outlines the analysis of safety issues followed the sequence of efforts. Since
the primary objective of this effort was to complete an FMEA for different fueling
options, the report focuses firstly on the selection of fueling options. Section 2 describes
hydrogen fueling station technology options, including the basic station types and their
associated requirements and tradeoffs, and the principal equipment. Section 3
addresses hydrogen fueling station permitting (including potentially applicable codes
and standards), procurement and contracting, installation, training, and related subjects.
Finally, Section 4 provides documentation of the fueling system, followed by a
comparison of the safety issues associated with gaseous and liquid fuels. This order of
presentation is appropriate for the experienced reader. Table 1-2 depicts a reading
order for readers not familiar with hydrogen fueling equipment or fuel safety issues.
1-7
Table 1-2. Report Organization and Contents (recommended flow for reading
new to hydrogen-based refueling and safety issues)
Report Section Description
Section 5
Comparison of
Safety Issues for
Hydrogen and Other
Fuels
0 25 50 75 100
Hydrogen
Natural Gas
Air
Methanol
Propane
Ethanol
Gasoline
Diesel
Vapor Molecular Weight (g/mole)
Determine fuel properties
Compare flammability hazards
Describe risk scenarios
Identify other safety issues
Station Type Fuel
1
2
3
4
5
Liquid Hydrogen
On-Site Electrolysis
On-Site Reforming
Tube Trailer Delivery
CNG
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Natural Gas
Section 2
Fueling Station
Options
Define vehicle scenario
Determine fueling
requirements
Evaluate technology options
Identify equipment
requirements
NATURAL GAS
REFORMER
WATER
Section 4
Fueling Station
Documentation
FMEA Inputs
Review PFD, P&ID, Site Plan
Code constraints, system specifications
TIAX D13
P001-LH2
Process: Compressed Hydrogen Tube Trailer
Study Section: Hydrogen Storage
Design Intent: Store up to 30 kg of hydrogen at 6,250 psig
Date: J uly 10, 2003
No. Failure Mode Cause Effects Controls F C Recommendation
Section 3
Failure Modes and
Effects Analysis
19 Fill storage
tank on cold
day to 6,250
psig
Overheat gas
with sun
exposure
Overpressure
storage tank
MAWP 7,333
psig
Maximum
pressure due
to thermal
expansion is
7,290 psig
based on 50C
increase in
temperature
M L
20 Relief device
failure (on
cylinders) fails
open
Mechanical
Failure
Release of
hydrogen to
atm via vent
stack
Vent stack is a
minimum of 15
feet above
ground
L L Storage system
should contain
relief devices
21 Storage tank
failure
Mechanical
failure,
corrosion,
hydrogen
embrittlement
Release of
hydrogen to
atm and
potential fire or
explosion
Storage tank
MAWP 7,333
psig
L H
Structured review
of safety issues
Develop
recommendations
Section 6
Conclusion
Summarize the objectives of the report, key findings, and present over-
arching recommendations
2-1
2. FUELING STATION OPTIONS
For this study, FMEAs were conducted for hydrogen fueling stations with similar design
criteria but different supply options. This approach should be useful to organizations that
need to build a hydrogen fueling station, even though the design criteria may differ from
those selected in this study. Where feasible, the fueling station designs considered in
this study reflect possible future design choices that may prove challenging to the
fueling station developer. Integration with gasoline fueling equipment was assumed for
the hydrogen fueling stations. When applicable, more energy efficient design choices
were assumed for the hydrogen supply equipment, although existing fueling stations do
not typically use such equipment.
A variety of configurations are candidates for hydrogen fueling systems. They will differ
in terms of fueling capacity, hydrogen supply option, level of integration with
surrounding infrastructure, and fueling equipment technology. The report on hydrogen
fueling station installation guidelines prepared by the project team reviews the
differences between different hydrogen supply options (Powars). Several studies also
document the costs and energy consumption for different supply options (ADL, Lasher).
A total of five types of fueling stations were considered for the FMEA study. Table 2-1
summarizes the five types of stations.
Developers are pursuing many other hydrogen supply options and facility
configurations. Among other supply options are pipeline delivery, mobile fuelers, on-site
liquid fuel (methanol, ethanol, ammonia, LPG, etc.) reforming and chemical hydrides,
chemical reactants. The project team and sponsors selected the supply options in Table
2-1 based on their uniqueness, observations on the type of fueling stations that are
being installed and studied in fueling station development programs, and the ability to
obtain detailed information on each fueling station type. Analysis of similar options such
as on-site reforming of natural gas and LPG was avoided. Resource limitations
prevented the project team from addressing other supply options.
Table 2-1. Fueling Station Options for FMEA Study
Fuel Station Type
Hydrogen 1. Liquid hydrogen delivered and stored onsite, gas compressor
Hydrogen 2. Onsite electrolyzer, 10-atm output, gas compressor
Hydrogen 3. Onsite steam methane reformer (SMR), 10 atm output, gas compressor
Hydrogen 4. Compressed hydrogen delivered onsite by tube trailer, gas compressor
Natural Gas 5. Compressed natural gas (CNG), gas compressor
2-2
2.1 Fueling Station Equipment
Gaseous fuel stations typically include equipment for the supply, compression, storage,
and dispensing of fuel. Figure 2-1 presents an overview of the general components of
the fueling stations considered in the FMEA analysis. The designations in Figure 2-1
and Table 2-1 are used to track the FMEA scenarios in Section 3. Section 4 includes
details of the station configuration, site requirements, and equipment.
B. High Pressure
Compression
On-site Generation of
Gaseous Hydrogen
2A. Electrolyzer
3A. Steam Methane
Reformer
r
Hydrogen Delivery
and Storage
1A. Liquid - LH2
4A. Gas - Tube Trailer
C. High Pressure
Storage
D. Vehicle
Refueling
Dispenser
Figure 2-1. Key Components of Hydrogen Refueling Stations
2.1.1 Delivery from Central Hydrogen Plant
Liquid Hydrogen
Liquid hydrogen is delivered to the fueling station by a cryogenic tank truck and
transferred as a liquid to an above ground station tank. Since liquid hydrogen is denser
than compressed gas, considerably more hydrogen is transported as a liquid in tank
trucks than as a compressed gas in tube trailers. The delivered liquid is maintained at
approximately 250C (420F) in a vacuum-jacketed vessel at the station. For the
station design considered in the FMEA, the hydrogen passes through a compressor and
is stored in pressure vessels. The liquid can be warmed in a heat exchanger and
converted to gas before being compressed or drawn from the liquid tank vapor space
and fed to the compressor.
Compressed Gas Tube Trailer
Several compressed gas delivery strategies have been developed for hydrogen vehicle
fueling. These include mobile fuelers, or refuelers, with and without on-board
compressors, as well as conventional tube trailer delivery of hydrogen. Conventional
tube trailer delivery with on-site compression was analyzed. Tube trailer delivery can
serve as a transition strategy while equipment for other delivery options is procured.
The option also requires a relatively low-capital expense for the hydrogen supply.
2-3
Hydrogen gas is delivered to the fueling station in a tube trailer, a pack of pressurized
cylinders initially at 217 atmospheres, or atm (3,200 psi) connected by a manifold, which
is hauled by a tractor truck. The hydrogen is transferred from the tube trailer by a
compressor to buffer storage tanks at 425 atm and then dispensed to the tank of the
vehicle. The trailer assembly is not a permanent fixture and is refilled off-site.
Connections to the trailer utilize flexible hose.
2.1.2 On-Site Hydrogen Production
Electrolysis
Electrolysis is the process of using electric energy to produce chemical changes. For
hydrogen production, an electric current is passed through an electrolysis cell
containing water and an appropriate electrolyte. Hydrogen gas is produced at one
electrode (cathode) and oxygen gas is produced at the other electrode (anode). The
gases are collected in separate collection chambers and compressed or vented as
required.
Alkaline and solid polymer electrolyte membranes (SPEM)
1
are the two most common
methods of electrolysis used for hydrogen production. For the FMEA, the electrolyzer-
based hydrogen refueling station is an alkaline electrolyzer. Alkaline is the oldest
electrolysis technology and the one most typically used for large-scale electrolytic
hydrogen production. A 10 atm electrolyzer was considered in the FMEA. Most
electrolyzers in todays fueling applications operate at atmospheric pressure. More
advanced designs operate at elevated pressures in order to reduce compression energy
requirements. Alkaline electrolyzers operate at temperatures between 80 and 145C.
Steam Methane Reforming
In a steam reformer, hydrocarbons react with water vapor to make hydrogen. The initial
reaction products are principally hydrogen plus carbon monoxide, which react with
additional water vapor in a shift reactor to produce hydrogen plus carbon dioxide.
Natural gas is the most commonly used feedstock, although reformers can be designed
to process almost any hydrocarbon. Steam methane reformers use methane (the
principal constituent of natural gas) and steam to generate hydrogen. The overall
reaction can be written as:
CH
4
+ 2H
2
O CO
2
+ 4H
2
1
Also referred to as proton exchange membrane (PEM)
2-4
The reformer operates typically around 800C. This temperature is achieved by
combusting waste gas and natural gas. A reformer system includes gas clean up and
hydrogen purification systems. The reformer system considered in the FMEA operates
at 10 atm and provides 10 atm reformer product (reformate) to a pressure swing
adsorption (PSA) system which separates most of the hydrogen from the reformate
stream. The PSA system provides high purity hydrogen to the compressor at close to
10 atm, which reduces the energy requirements for the hydrogen compressor. This
configuration represents a more state-of-the-art design than reformers that operate at
atmospheric pressure and one more typical in current installations. The high-pressure
reformer represents a more common future design.
2.1.3 High Pressure Compression
The physical properties of hydrogen, fuel purity specifications for fuel cell vehicles,
hydrogen supply, and vehicle fueling pressure affect the requirements for compressors.
Section 4 discusses compressor requirements, which vary among the hydrogen and
CNG supply options. The principal factors to consider in a fuel station design include the
type of compressor, motor, and pressure requirements. Compressor design options
include the cylinder lubrication system, cooling system, motor, and piston configuration.
For hydrogen compression, oil-free compressors are generally preferred over oil
lubricated designs because lubricating oil is a source of contamination for the hydrogen.
Cooling between compression stages can be accomplished with air or coolant. A piston
compresses the gas in each stage. The gas is then cooled before it enters the next
stage. For passenger cars fueling at 340 atm (5,000 psi), the hydrogen compressor
would need to provide hydrogen at up to 425 atm (6,250 psi). CNG is stored at 305 atm
(4,500 psi) for vehicle fueling at 245 atm (3,600 psi).
In the configuration for this study, the compressor feeds the high-pressure storage
tanks, which in turn feed the dispenser for fast-fill fueling. Typical hydrogen
compressors will have more stages than CNG compressors because of higher output
pressure and the physical properties of hydrogen. The gas properties of hydrogen also
affect the exit temperature for each compression stage. Compressors need to be
designed to limit the exit temperature for each stage in order to prevent thermal
stresses.
The compressor exit temperature needs to be limited to approximately 300F to insure
long piston life. Diaphragm compressors are an alternative to piston compressors.
Diaphragm compressors are often preferred for hydrogen service because they tend to
provide a better seal than piston compressors.
2.1.4 Compressed Gas Storage
All fueling station designs considered in the FMEA include high-pressure gas storage
prior to the dispenser. The capacity varies among the different supply options.
2-5
Hydrogen is stored at a nominal pressure of 425 atm (6,250 psi) for vehicle fueling at
340 atm (5,000 psi). CNG is stored at 305 atm (4,500 psi) for vehicle fueling at 245 atm
(3,600 psi). The fuel storage is configured in a cascade system with gas stored in three
separate vessels in order to provide fast fill fueling.
2.1.5 Vehicle Fueling Dispenser
The fueling dispenser contains controls, fuel metering, and a connection for the fueling
hose. It draws fuel from the cascaded high-pressure gas storage system. The controls
on the dispenser determine the final fill pressure on the vehicle. The dispenser meters
the quantity of fuel transferred to the vehicle to achieve the design pressure, (340 atm
for hydrogen, 245 atm for CNG) at 20C (68F). Section 4 describes the approach for
achieving temperature compensated filling differs for hydrogen and CNG stations. The
dispenser uses a heat-of-compression algorithm to predict the gas quantity needed to
provide a full fill, or the fullest possible fill, within tank pressure and temperature
constraints. The fueling nozzles have a lever that actuates a three-way valve allowing
gas (that would otherwise be trapped at the end of the fill) to be vented back to the
dispenser through a vent hose. This lever makes it easier to disconnect the nozzle and
minimizes the leakage of flammable hydrogen from the nozzle and receptacle when the
nozzle is removed.
2.2 Fueling Station Design Basis
The different fueling stations under consideration share a common design basis. Tables
2-2 and 2-3 present the design basis and salient operating characteristics selected for
the FMEA.
The fueling capacity is based on filling ten (10) hydrogen or CNG vehicles per day.
Table 2-2 shows how the fuel fill rates reflect vehicle fuel economy and driving
assumptions.
2-6
Table 2-2. Refueling Station Common Design Bases
Hydrogen CNG
Number of vehicles refueled 10 per day
Amount of fuel per fill 3 kg (1270 scf) 15.4 kg (743 scf)
Driving per fill 185 km (115 miles)
Vehicle refueling time 10 min/fill
Station average consumption 30 kg/day 7430 scf/day
Nominal dispensing capacity 5 vehicles in 2 hours
Typical fuel consumption (gasoline equivalent) 4 L/100 km (60 mpg) 7.9 L/100 km (30 mpg)
Table 2-3. Refueling Station Characteristics
Refueling System
Liquid
Hydrogen Electrolyzer SMR
Tube Trailer
Delivery CNG
Fuelings/day 10 10 10 10 10
(kg/h) 3.7 1.2 1.2 3.7 18
Compressor Flow
Rate
(scfm) 26 8.6 8.6 26 15
(psi) 6,250 6,250 6,250 6,250 4,500
Fuel Station Storage
Nominal Pressure
(atm) 425 425 425 425 305
(psi) 5,000 5,000 5,000 5,000 3,600
Vehicle Storage
Nominal Pressure
(atm) 340 340 340 340 245
Storage type Cascade Cascade Cascade Cascade Cascade
Storage capacity, gas (kg fuel)
a
24 48 48 24 120
Storage volume (m
3
) 0.82 1.6 1.6 0.82 0.49
a
Storage meets the following constraints: Fuel 5 vehicles in 2 hours with 30% cascade efficiency,
taking into account compressor flow rate. For Electrolyzer and SMR, provides sufficient storage for
24 hours production, taking into account dispensing fuel onto vehicles.
2.3 Fueling Station Documentation Failure Modes and
Effects Analysis (FMEA) Perspective
Section 3 describes the FMEA process in detail. The FMEA is typically part of an overall
safety plan. With the help of the FMEA, the safety plan identifies failure modes for
equipment and processes, the consequences of such failures, and evaluation of existing
controls and recommendations of additional controls to mitigate the risk of the identified
failure modes. The FMEA is an ongoing process and must be updated every time
design or process changes are made.
2-7
The FMEA presented for each of the five stations in this report has a functional top-
down approach that is generally applicable to similar stations. Such an approach is
appropriate when specific details of the fueling station components presented earlier are
not present (and vary from station to station). While there are no standard guidelines for
this level of information/documentation requirements for a top-down FMEA, the
following documentation was prepared for the FMEA for the purposed of this study:
Process flow diagram (PFD)
Simplified piping and instrumentation diagram (P&ID)
Site plan
Standard operating procedures
Safety standards and codes
It must be noted that the documentation reference above were of a very generic nature
since no specific existing or planned station was under consideration. Instead, this
FMEA targets all stations of a particular type and identifies the most common and
minimum set of failure modes that must be of concern from a safety perspective. It
should be the responsibility of the designers and operators of such stations to conduct a
detailed FMEA covering at least the failure modes considered here.
Section 4 presents summaries of documentation packets for each station type. Each
packet includes a brief description of the process regarding the fuel generation. In
addition, there is technical material regarding the design and layout of individual
stations. Section 4 also lists equipment used and its specifications, and a process flow
diagram (PFD) showing the order of the material flow in the system. The report also
contains a generic piping and instrumentation diagram (P&ID). Finally, it includes a
chart of codes and standards regarding fuel storage as well as a site plan layout for the
fueling station with regard to the aforementioned codes and standards. The FMEA team
had access to more detailed design information from several actual hydrogen fueling
stations. The team used the design information to confirm study assumptions about the
operation of subsystems in the fueling station.
3-1
3. FAILURE MODES AND EFFECTS ANALYSIS
A FMEA is a systematic and structured method of identifying product and process
problems, assessing their significance, and identifying potential solutions that reduce
their significance. The objective of a FMEA is to look for all the ways a product or
process can fail (failure modes). Each failure mode has a cause and a potential effect.
Some failure modes are more likely to occur than others, and each potential effect has a
relative risk associated with it. The FMEA process is a way to identify the failure modes
within a process or product and to identify actions to reduce the severity, occurrence, or
eliminate the cause of the failure mode. In general, the FMEA process follows a
standard procedure, as detailed below:
1. Identify top level hazards/events
2. Identify related equipment/components/processes
3. Identify potential failures
4. Identify design safety
5. Identify corrective actions
An FMEA can be performed using two different approaches. The hardware, or
component, analysis is the identification and analysis of ramifications of component
failures. This method is a bottom-up approach, wherein failures are initiated on the
subsystem level. The functional approach is a top-down method, more suitable when
specific components have not yet been chosen. Industry uses both approaches. The
development of the FMEA is a continuous process, and the document should evolve as
the system design changes.
In a FMEA, the relative risk of a failure and its effect is determined by three factors:
Occurrence the probability or frequency of the failure occurring
Severity the seriousness of the effect of the failure mode
Detection the probability of the failure being detected before the impact of the
effect is realized
In a typical FMEA, numerical rankings are assigned for each factor. The higher the
ranking, the greater the potential harm posed by the failure and its effect. These
rankings can be used on any scale desired. Many organizations performing FMEAs use
a scale of 1 to 10; others use 1 to 5. Most FMEA practitioners believe that the minimum
resolution for the scale should be 1 to 3. FMEAs are teamed-based. In performing a
FMEA, a team is assembled of four to six individuals knowledgeable in various aspects
of the process or product under evaluation.
The FMEA process consists of the FMEA team meeting and brainstorming on potential
failure modes of the process or product, and identifying the cause(s) of the failure, the
effect(s) of the failure and the current controls in place to detect the failure before the
effect occurs. Having all the potential failure modes identified with associated causes,
effects, and current controls, the FMEA team then assigns occurrence, severity, and
3-2
detection rankings to each combination. Consensus must be reached for the process to
be effective. The overall measure of relative risk in a FMEA is termed the risk priority
number (RPN). The RPN is the product of the three factors: occurrence; severity; and
detection. RPNs can then be used to rank the significance of the risk posed by the
failure/effect and the need for corrective actions to reduce or eliminate the potential
failure mode.
As noted in the introduction section, this study is a top-down functional analysis of five
types of fueling stations. Given the time and resources available for the project, a high-
level FMEA was the objective of this project. The intent of this report, as stated earlier,
is to facilitate the basic understanding of the following:
Key engineering components and operating features of the five types of fueling
stations
Major failure modes associated with the key components and operation of the
fueling station
Rank relative risk of different hazard scenarios
A FMEA team comprised of five persons (on average) analyzed each of the five types of
fueling stations. Prior to starting the first FMEA, the team agreed to follow a three-point
scale of low (L), medium (M), and high (H) to rank the factors determining the relative
risk of potential failures. The risk level of a particular failure mode was to be determined
by assigning a scale-letter to the frequency of occurrence (F) of the failure mode and
the consequence of the failure mode (C). The third factor, detection (or control or
remedial action, R), was not assigned a letter-scale.
Detection (or control) defines what safety mechanisms are in place to prevent the failure
mode from occurring. The key reason for not assigning risk to detection is that hydrogen
fueling stations are not common place and there are no established safety standards
specific to their installation and operation, and the few existing stations adopt general
good engineering practices. Therefore, the team believed that by assigning a risk level
to detection could lead to its misinterpretation as a standard practice. Consequently, for
this study, an RPN was not calculated for each failure mode. Instead, for specific high-
risk failure modes, the team provided recommendations to mitigate the risk.
Table 3-1 describes the high, medium, and low ratings. The rating for frequency or
consequence for a particular failure mode may be the result of a number of other
activities, each of which carries with it a risk-level rating. The cases where the high-level
rating stems from the individual component events are discussed in detail as they occur
in the following sections under each fueling stations FMEA.
After the team completed the FMEA, they discussed the risks for each scenario
according to the key failure modes (fires, shock hazard, etc.) and then reviewed ranked
failure modes with the highest risk ratings.
3-3
Table 3-1. Frequency and Consequence Ratings
Frequency Rating Description
High (H) Almost certain to occur repeatedly
Medium (M) Likely to occur to rarely likely to occur
Low (L) Unlikely that failure would occur
Consequence Rating Description
High (H) Potential for great harm or death if
someone is present within the impact
area.
Medium (M) Harm would require some medical
treatment to some pain or discomfort if
someone is present within the impact
area
Low (L) End user, if present, would not notice
A risk-binning matrix summarizes the consequence and frequency ratings for each
FMEA. Risk-binning is one analysis tool for risk mitigation recommended by DOE for
hydrogen projects. Each hazard is plotted on a frequency vs. consequence matrix,
which indicates its level of risk: high, moderate, low, or negligible. High risks are
considered combinations of M x H, H x M, and H x H ratings. Moderate risks are
combinations of L x H, H x L, and M x M. Finally low risks are combinations of L x M, M
x L, L x L, and no safety hazard or negligible risk scenarios. Table 3-2 presents the
format of a risk binning matrix.
Section 2 notes that the typical hydrogen fueling station can be categorized into four
sections: hydrogen production or delivery, high-pressure compression, high-pressure
storage, and dispensing. Of these, dispensing hydrogen to the end user is common to
all four types of hydrogen stations discussed in this study, and the associated
component and operational issues are uniquely similar. Consequently, the FMEA for the
dispensing section for each type of station is identical. Similar scenarios are highlighted
in the FMEA worksheets. High-pressure compression and high-pressure storage are
also functionally similar for the four types of stations; however, there are minor
engineering design, equipment, and operational differences. The source of hydrogen
(on-site production or delivery) is clearly different for each of the four types of stations
and is the distinguishing feature of each type of station.
Table 3-3 presents combustion-related properties of hydrogen and compares it with
other fuels. While there are differences in each type of station, the over-riding safety
issues are the explosive and flammable properties of hydrogen. Other safety issues
arise from the presence of high- pressure storage tanks. Asphyxiation hazards,
electrical shock hazard, cryogenic and high temperature hazards from equipment were
3-4
also considered. All failure modes in this FMEA are associated with incidents leading to
human injury or death. All of these failure modes apply to one of the various elements of
the four sections of a station.
Table 3-2. Risk-Binning Matrix
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
Unlikely Likely Anticipated
High
(H)
X X X
Medium
(M)
X X X
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
X X X
X = Number of occurrences
Table 3-3. Combustion Properties of Hydrogen, Natural Gas and Gasoline
a
Property Hydrogen Natural Gas Gasoline
Flammability limits in air 4.1 - 75% vol 5 15% vol 1.4 7.6% vol
Minimum ignition energy 0.02 mJ 0.29 mJ 0.24 mJ
Burning velocity in NPT air 2.7-3.3 m/s 0.4 m/s 0.35 m/s
Flame temperature in air 2045C 1877C 2207C
Gas molecular weight 2.016 16.5 17.5 68 - 80
a
See documentation in Section 5.
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-5
Commonality
Section 3.1 through 3.5 presents the results of the FMEA for each fueling station type.
Processes common to the five stations are high-pressure storage and dispensing.
Consequently, the results of the FMEA for these components are also similar; however,
we chose to report these results repetitively for the five station types so that each
station can be examined in a stand-alone fashion.
Tables 3-4 through 3-13 present the results of the FMEA. While commonalities in
design and process exist, the options for several distinct design choices also exist.
Specific risk scenarios that would be affected by other design choices are indicated by a
symbol in the FMEA results table (3-4, 3-6, 3-8, 3-10, and 3-13). For each failure
mode, specific recommendations are made wherever applicable to eliminate the failure
mode or to lower the risk level.
3.1 Liquid Hydrogen Refueling Station FMEA
3.1.1 General Description
The liquid hydrogen station for which an FMEA was performed had the following key
components:
Hydrogen Delivery
LH
2
Storage Tank
Vaporizer/Heat Exchanger
High-pressure compressor
High-pressure storage
Dispenser
Section 4.1 presents a detailed description of a typical liquid hydrogen-based refueling
station.
3.1.2 FMEA Results
Table 3-4 presents the results of the FMEA. The FMEA evaluation followed the four
major functions (supply, compression, storage, and delivery) required in a hydrogen
fueling station. The liquid hydrogen delivery and storage (Section 1A) is unique among
the supply options in this report. Liquid hydrogen converted to high-pressure gas with a
compressor involves similar equipment for the other hydrogen supply options. The
storage and dispensing equipment is also similar to the other fuel supply options. Risk
scenarios, which would be affected by other design choices, are indicated with a
symbol.
3
-
6
Table 3-4. Liquid Hydrogen Station FMEA Results
Date: J uly 7, 2003
Process: 1. Liquid Hydrogen
Study Section: 1A. Liquid Delivery, Storage, and Vaporization
Design Intent: Unload and store 2,000 gal of liquid hydrogen at 10 psig and 420F
1 Liquid trailer leak Mechanical failure due to
road vibration
Potential fire Unloading inspection by
station rep or driver
Hydrogen leak detectors in
area
M L
2 Liquid trailer leak Vehicle impact to truck
while unloading damages
hydrogen piping
Potential fire/explosion Driver puts caution cones
around truck.
M M Establish separation
distance of vehicles
from unloading truck.
3 Unloading hose
connection leaks
Mechanical failure or
improper connection
Cryogenic burn Unloading is continuously
monitored by both driver and
station rep. Driver wears a
Nomex suit.
M L Implement a leak
check prior to
unloading.
4 Release from
connecting hose
Hose not vented prior to
disconnect human error
Cryogenic burn Driver training and unloading
checklist, using standard
established procedures for
unloading cryogenics
L M
5 Overfill storage tank Human error or instrument
failure. Truck may contain
up to 10,000 gal of
hydrogen and only 2,000
gal might be unloaded to
storage tank
Liquid hydrogen release from
pressure relief valve with
potential fire
Driver training and
unloading cryogenics
H M Review procedures
for verifying tank fill
level in safety plan.
6 Inner storage tank
leak
Mechanical failure Loss of vacuum between
inner and outer vessel.
Release from outer vessel
pressure relief device set at
0 psig
PSV vents at elevated
location
L L
3
-
7
7 Overpressure
storage tank
Normal boil off due to low
vehicle filling (no vehicle
fills in 2 weeks)
Release from pressure relief
valve
Design system to allow for
wide storage pressure range
in LH
2
tank
M L Identify alternate use
of boil off
8 Overpressure
storage tank
Loss of vacuum from the
liquid storage tank jacket
vacuum
Release from pressure relief
valve. Exceed capacity of
PSV and blow rupture disc
and vent entire contents of
tank.
PSV vents at elevated
location
High pressure indication on
storage tank
M M Monitor tank
pressure rise to
detect soft vacuum
9 Heat exchanger
failure (vaporizer)
Icing on outside causes
loss of heating
Cold vapor causes blow-by of
compressor seals and is
vented to stack
Stack vents at elevated
location
NFPA 50B requires a low
temperature shutoff switch or
valve in the vaporizer
discharge piping
L L Compressor should
stop if supply
temperature is too
cold
10 Valve to pressure
build circuit closed
Pressure regulating valve
fails
Damage compressor seals Low pressure switch shuts
down compressor
L L
11 Overpressure liquid
hydrogen piping
Blocked in line filled with
liquid
Fail line and release of liquid
hydrogen and potential fire or
explosion
Hydrostatic relief valve L M Verify all potential
sections of line that
can be blocked in
have hydrostatic
relief
Study Section: 1B. Hydrogen Compression
Design Intent: Heat hydrogen from 420F and compress 3.7 kg/h of hydrogen from 10 psig to 6,250 psig
12
Compressor suction
line failure
Mechanical failure of line or
fitting
Release of hydrogen and
potential fire
Hydrogen detectors, area
electrical classification,
compressor in open area
L M Piping in the entire
system should be
designed to ASME
B31.3 code
13 Cooling system
failure
Loss of cooling fluid Reduce piston life above
300F
No safety hazard
_ _
3
-
8
14
Lubrication system
failure
Loss of fluid Compressor failure and
hydrogen leak with potential
fire
Low oil pressure shutdown L M
15
Seal failure Mechanical failure Release of hydrogen and

potential fire
Seal failure alarm on
compressor
L M
16 Compressor suction
or discharge valve
failure
Mechanical failure No safety hazard _ _
17 Pressure relief
device fails open
Mechanical failure Relief valves are vented to
vent stack.
No safety hazard
_ _
18 Valve on discharge
of compressor fails
closed
human error and failure of
pressure relief valve to
open
Overpressure compressor
and rupture line, release of
hydrogen and potential fire
electrical classification
L M
19 High pressure
(6,250 psig)
hydrogen supply line
failure
Mechanical failure Release of hydrogen and
potential fire
L M
20 Compressor suction
line failure
Mechanical failure of line or
fitting
potential fire
L M
Study Section: 1C. High pressure storage
21
Fill storage tank on

cold day to 6,250
psig
Fill storage tank on cold
day to 6,250 psig
Heat stored gas during day
Overpressure storage tank
MAWP 7,333 psig, RPV
releases hydrogen with
potential fire or explosion
Maximum pressure due to
thermal expansion is 7,290
psig based on 50C increase
in temp.
M M Review climate
conditions in safety
plan
3
-
9
22 Relief device failure
(on cylinders) fails
open
Mechanical failure Release of hydrogen to atm
via vent stack and potential
fire or explosion
Vent stack is a minimum of 5
meters above grade.
L L Storage system
should contain
redundant relief
devices.
23 Storage tank failure Mechanical failure,
corrosion, hydrogen
embrittlement
Release of hydrogen to atm
and potential fire or explosion
Storage tank MAWP 7,333
psig
L H Storage system
should contain
redundant relief
devices
24 Piping leak Mechanical failure Release of hydrogen to atm
NFPA 50A setback
distances
L H
25 Compressed gas
storage tank failure
External fire due to large
spill of gasoline from
delivery truck
Potential failure of tank due to
overheating of metal
Compressed gas is stored in
classified area with LH
2
storage tank. NFPA 50B
requires systems within 50 ft
of above ground storage of
flammable liquids to prevent
accumulation of flammable
liquids under the hydrogen
system. Hydrogen system
must also be at least 75 ft
from the fill or vent line on
any underground gasoline
tanks.
L H Design and codes
should consider
stations dispensing
both hydrogen and
gasoline.
Study Section: 1D. Hydrogen Dispensing
Design Intent: Dispense up to 3 kg of hydrogen per vehicle at either 3,600 or 5,000 psig in 10 min
26 Piping failure Vehicle impact to dispenser Potential fire or explosion Bollards around dispenser L H
27 Dispenser cascade
control failure
Pressure relief device on
dispenser and storage
tanks fails
Overpressure vehicle fuel
tank
Relief valve on vehicle tank
vents
L H
3
-
1
0
28
Use wrong pressure

nozzle (5,000 psig
vs 3,600 psig)
Human error Potential overpressure of
vehicle fuel tank
Nozzles designed to prevent
5,000 psig nozzle to be
attached to a 3,600 psig tank
L M
29 Drive away while
connected to
dispenser
Human error Rupture hose and potential
fire or explosion
Break away connection with
poppet isolation valves
L M
30 Hose failure Mechanical failure Potential fire or explosion Hoses rated for about 8,000
psig
L M Should be tested or
inspected on a
regular basis
31 Leak in connection O-ring damaged or nozzle
damaged
Potential fire Dispenser conducts leak
check prior to each fill.
M L
32 Vehicle pressure
relief device leaks
Mechanical failure Potential fire or explosion Relief valve on vehicle tank
vents.
L M
33 Fail to vent nozzle
before disconnecting
Human error No safety hazard Venting before disconnecting
is automatic, and is built into
the nozzle.
_ _
34 Fuel nozzle vent
lever open while
filling
Human error Potential fire or explosion Three-way valve is designed
to only flow fuel when
connected to vehicle.
Foreign matter from
dispenser could
L M
35 Nozzle leaks after
disconnect
Mechanical failure Potential fire Dispenser valve closes L M
36 Vehicle tank
isolation valve leaks
Mechanical failure and
leaking check valve
Potential fire L M
3-11
Key parameters affecting safety include:
Equipment located outdoors where hydrogen leaks would escape to the atmosphere
Site layout and equipment meets NFPA 50A and NFPA 50B requirements
Liquid hydrogen equipment is in a fenced area. Only trained personnel have access
to the liquid hydrogen, compressor, and storage equipment.
Liquid hydrogen storage, compressor, and dispenser in Class 1, Division 2 areas
(Explosion proof equipment)
Fuel dispenser uses CAFCP communication to fill protocol for temperature
compensated vehicle filling. If vehicle is not equipped for communication fill,
maximum fill pressure is 340 atm (5,000 psi).
Key Failure Modes
Broadly, failure modes can be grouped into situations involving:
1. Exposure to spills and leaks of the cryogenic-liquid
2. Ignition of hydrogen gas from leaks and vaporization of spills
3. Mechanical failure of high pressure equipment
The FMEA team limited the analysis to failure modes considered both realistic and
representative of the types of hazards that could occur at a fueling station. The team
observed that risk scenarios involving asphyxiation hazards would also involve ignition
hazards. Asphyxiation hazards were not analyzed because ignition hazards occur at a
lower hydrogen concentration than asphyxiation hazards. The reader should be aware
that the potential for asphyxiation hazards in enclosed spaces occur in situations where
large volumes of liquid hydrogen are released. Intentional misuse, catastrophic
environmental events, and vandalism were also not analyzed.
Cryogenic burns can occur during fuel unloading and facility operation. A fence and
warning signs prevent public access to cryogenic equipment. Only trained personnel
following appropriate safety protocols are permitted to access the cryogenic equipment.
Liquid hydrogen leaks and spills can occur at various points along the fueling-chain
such as: damage to the liquid-hydrogen tanker truck delivering the hydrogen; damage to
the liquid hydrogen transfer equipment such as hoses and fittings; overfilling of the on-
site liquid hydrogen tank; failure of the on-site storage tank; and failure or malfunction of
the associated components such as the cryogenic compressors/pumps, heat
exchangers, valves, piping, and instrumentation. In addition to being a combustion
hazard, the consequences of a liquid hydrogen leak/spill are severe cryogenic burns
that may be caused to personnel who are working with the equipment.
Gaseous hydrogen leaks and venting also pose risks through the ignition of the
hydrogen. Gaseous hydrogen leaks along the fueling system can occur due to:
evaporation of liquid hydrogen from the leaks/spills described above; failure of the high-
pressure compressor; damage to the high pressure storage tanks; damage to
3-12
dispensing equipment; damage to the piping and valves; and human errors such as
vehicle drive-away with the dispensing hose still connected and careless behavior
during refueling.
Failure Mode Ranking
Table 3-5 categorizes all of the scenarios from the FMEA by combined frequency and
consequence rating in a risk-binning matrix. This allows for identification of the
prioritization of safety improvement efforts for the fueling system.
Liquid Hydrogen Delivery and Storage
The FMEA team assigned a high (H) frequency risk rating to only one failure mode,
which was the overfilling of the onsite liquid hydrogen storage tank (No. 5, Table 3-4).
Filling the liquid level above the design capacity of the tank could result in a situation
where the vapor in the tank condenses and the liquid expands beyond the tank
capacity. Liquid hydrogen expands as heat enters the tank and pressure rises. Liquid
hydrogen truck operators are trained in the proper procedures for filling stationary tanks
to avoid an over fill situation; however, an H frequency was assigned to this scenario
3-13
Table 3-5. Risk-Binning Matrix Liquid Hydrogen Delivery, Compressed Gas
Fueling
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
High
(H)
5 0 0
Medium
(M)
15 3 1
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
4 4 0
because of the potential for human error. Implementing procedures to assure that the
tank is not overfilled would reduce the risk associated with this scenario.
If this failure mode were to occur, it would result in the release of hydrogen from the
pressure relief valves and in a fire if an ignition source were present. The FMEA team
did not identify any controls that would prevent this failure mode from occurring in the
first place and assigned a medium (M) risk rating to the consequence of this failure
mode. Under the FMEA methodology followed here, the failure mode with the highest
risk would have a risk assignment of HH (for F and C respectively) and the lowest would
have an assignment of LL. For the liquid hydrogen station, the tank overfill attained the
worst case status with a risk designation of HM.
Three failure modes associated with the failure of the liquid hydrogen storage tank,
piping, and compressed gas tank received an H rating for the resulting consequences,
since failures in liquid or gaseous storage tank could result in a fire or explosion. A low
(L) risk of occurrence resulted in an HL rating. The quantity of gas stored in a liquid
hydrogen tank (2,000 kg) represents much more fuel energy than the quantity of gas
stored in compressed gas tanks. Consequently, the set back distances in NFPA 50B for
liquid hydrogen are also greater than related distances in NFPA 50A for compressed
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-14
hydrogen. Tanks and storage vessels are protected with pressure relief devices, which
help assure that the tanks maximum allowable pressure is not exceeded.
Several failure modes received MM ratings. Table 3-4 indicates recommendations for
improving the risk ratings. For example, a collision of a car into a delivery truck that was
unloading could result in a hydrogen leak (Failure Mode No. 2). The location of the truck
unloading area, combined with the egress of automobile traffic to the site, is intended to
minimize the potential for damage to the truck while unloading. Nonetheless, the FMEA
team believes that the truck-unloading configuration indicated in the plot plan in Section
4 still allowed the potential for rare accidental collision. More improvements to the site
plan or procedures to prevent automobiles from entering the fueling station site during
fuel delivery would further reduce the risk.
Failure mode No. 8, also associated with the liquid hydrogen tank system, received an
MM rating. As in Scenario No. 5, liquid hydrogen is released from the tank vent. A loss
of vacuum in the liquid hydrogen tank can result in heat entering the tank and an
expansion of the fuel.
Compression, Storage, Dispensing
MM ratings were also assigned to scenarios in the fuel storage and vehicle dispensing
sections of the fueling station. These scenarios apply to all of the fuel supply options.
Both of these scenarios relate to an over pressure of the fuel tank and subsequent
release of hydrogen from the pressure relief valve or vehicle pressure relief device.
Under unusual weather conditions, the fueling station storage tanks can be filled while
very cold and then heated during the day (No. 21, Table 3-4). The range in ambient
temperature swings is taken into account in fueling station design; however, unusual
temperature variations are possible. A failure in the instrumentation associated with the
temperature compensation system could result in the overpressure of a vehicle tank
during fueling (No. 27, Table 3-4).
The consequence ratings for the hydrogen compression system were all M or lower. For
the liquid hydrogen system, the compressor is in the open and leaks would not have an
opportunity to accumulate. This consequence rating was assigned because the
equipment is located outdoors and leaking gas would rise away from the equipment and
not accumulate.
The existing controls or lack of any controls greatly influenced the consequence risk
rating for most failure modes. For example, in the cases where a hydrogen leak detector
was present as a control, the resulting consequence risk level was mitigated to either an
M or an L from an almost certain H in the absence of the control. The FMEA team
observed that engineering design -- either equipment, system or civil/architectural
design played an important role in the associated risk level. A simple example is the
case of bollards protecting dispensing and piping equipment, which significantly lowers
the frequency of catastrophic accidents from occurring.
3-15
Many of these top-level occurrences are a product of sub-events that individually may
have had an H-rating but were undermined by associated lower risk sub-events. A
single failure mode may be the result of a sequence of sub-events each of which has an
associated frequency of occurrence. In such cases, the relative risk rating that was
assigned by the FMEA team to the failure mode occurrence frequency was the sub-
event frequency with the lowest risk rating.
Typically, this sub-event would prevent other sub-events with higher risk-ratings from
materializing. For example, consider the scenario where a fire or explosion may occur
due to a vehicle drive-away during dispensing (No. 29, Table 3-4). This scenario is
unavoidable in all fueling station types because of the potential for human error. The
drive-away on its own was considered to be a relatively high frequency (H) event. For
ignition to occur under this failure mode, in addition to the drive-away, the break away
connection has to fail and the hose must rupture, followed by failure of the poppet
isolation valves. Finally, an ignition source must be present. At least two of the four sub-
events to drive away were assigned a low (L) frequency of occurrence and hence the
overall risk rating for the frequency of this failure mode occurring was assigned a low
(L). The frequency of occurrence for many of the failure modes resulted with L and M
designations by the FMEA team.
3.2 Electrolyzer Refueling Station FMEA
The electrolyzer station for which an FMEA was performed has the following key
components:
Electrolysis unit (electrolyzer cell and power system)
Pure water supply unit
Alkalization unit
Dispenser
Section 4.2 presents a detailed description of a typical electrolyzer-based hydrogen
refueling station.
3.2.2 FMEA Results
Table 3-6 lists the results of the FMEA evaluation. The FMEA evaluation followed the
four major functions (supply, compression, storage, and delivery) required in a hydrogen
fuel station. The hydrogen production process, which includes the introduction of a 34
percent KOH solution into the electrolysis cell, the production of hydrogen by
3-16
electrolysis of water, and the clean up of the hydrogen gas, is unique among the supply
options in this report. After production, the purified hydrogen stream is sent to a
compressor.
The pressurized (10 atm) electrolyzer selected for this study presents different safety
challenges than those from an atmospheric system. The assumed system has the
electrolyzer and compressor located in a ventilated enclosure. This strategy eliminates
the requirement for some classified electrical equipment. A similar strategy was
assumed for the SMR system. The storage and dispensing equipment is similar to the
other fuel supply options.
Electrolyzer and compressor located in a ventilated enclosure with hydrogen
detectors
Site layout and equipment meets NFPA 50A
Only trained personnel have access to the fuel production and compressor
enclosure. Public access to the storage equipment is also prohibited.
Storage tanks and dispenser in Class 1, Division 2 areas (Explosion proof
equipment)
Fuel dispenser uses CAFCP communication fill protocol for temperature
3
-
1
7
Table 3-6. Electrolysis Station FMEA Results
Date: J uly 8, 2003
Process: 2. Electrolysis
Study Section: 2A. Water Electrolysis, Hydrogen Generation
Design Intent: Generate 1.25 kg/h of >99.99% hydrogen at 150 psig by electrolysis of water
1. KOH leak Mechanical failure or
human error
Employee injury Operator wears rubber
gloves and face shield
Safety shower and eyewash
station in area
Polycarbonate shield around
cells
L M
2.
Exposed electrical
circuit 240 volts DC,
600 amps
Human error Employee injury Polycarbonate shield around
cells limits access
L H
3. Rectifier startup Human error
Turn unit on before
turning breaker on and
then contact rectifier
Employee injury L H Provide mechanism to
prevent turning power on to
unit until rectifier breaker is
on
4. Demineralizer failure Media is saturated or
deactivated
Sludge buildup in bottom of
cell, no safety hazard
Conductivity detector and
high conductivity shutdown
at one micro-Siemens
_ _
5. KOH pump failure Mechanical failure Low water level in cell and
high temperature damages
cell, no safety hazard
Low level shutdown
High temperature shutdown
_ _
6. Cell control failure Instrument failure
leading to stack failure
Cell damage with loss of fluid
and potential exposure
Low level shutdown
L M Provide caustic containment
sump and drain
3
-
1
8
7. Cell seal/demister
failure
Mechanical failure High oxygen level in
electrolysis gas, generate
high temperature in catalytic
purifier and potential internal
fire or explosion
Low level shutdown High
temperature shutdown on
oxygen header set at 70C
High differential temperature
(>40C) across catalytic
purifier
Oxygen analyzer and
shutdown on hydrogen line
downstream of demister
L H
8. Oxygen vent leak Mechanical failure Potential fire hazard (higher
than normal oxygen content)
Oxygen must be vented to a
safe location outdoors.
L L
9.
Hydrogen gas leak Mechanical failure and

loss of blower
Potential fire or explosion Enclosure is vented, at 20%
LEL alarm, 40% shutdown
Loss of blower shutdown
L H
10.
Catalytic purifier failure Fouling (may also

need failure in cell to
get high oxygen
concentration)
High oxygen in product
hydrogen, potential explosion
in compressor
Oxygen analyzer and
shutdown on hydrogen line
downstream of demister
(above 1% in 10 min, above
2% in 5 sec)
L H Provide oxygen analyzer
downstream of purifier
Evaluate upper flammable
limit for hydrogen in pure
oxygen
11. Molecular sieve dryer
failure
Mechanical failure,
unable to regenerate
High moisture in hydrogen
product, potential corrosion or
hydrogen embrittlement of
downstream equipment or
water slug to compressor
M L Provide a dew point
analyzer for hydrogen
leaving dryers
12. Venting electrolysis
gas
Normal startup Ignition of electrolysis vent Gas is vented to a safe
location.
L L
13. Electrolysis gas vent
valve leaks
human error
Air ingress to compressor
and potential explosion or
detonation (much more likely
for low pressure systems)
Low pressure shutdown on
compressor suction
L H
14. Cooling system failure Catalytic purifier
aftercooler failure
Leak of hydrogen into cooling
system and potential fire or
explosion in surge tank
Gas is vented to a safe
location
L M Provide LEL detector on
cooling water surge tank
vent. Vent must be in a safe
location.
3
-
1
9
Date: J uly 8, 2003
Design Intent: Compress 1.25 kg/h of hydrogen from >80 psig to 6,250 psig
15.
Compressor suction
line failure
Mechanical failure of
line or fitting
Enclosure is vented, at 20%
L H Piping in the entire system
should be designed to
ASME B31.3 code.
16. Cooling system failure Loss of cooling fluid Reduce piston life above
300F
No safety hazard
_ _
17.
Lubrication system
failure
Loss of fluid Compressor failure
and hydrogen leak with
Low oil pressure shutdown
L H
18.

diaphragm compressor
L H
19. Compressor suction or
discharge valve failure
20. Pressure relief device
fails open
Mechanical failure Relief valves are vented back
to ballast or blow down tank
No safety hazard
_ _
21.
Valve on discharge of
compressor fails
closed
human error and
failure of pressure
relief valve to open
and rupture line. Release of
explosion
L H
22.
High pressure (6,250

psig) hydrogen supply
line failure
ASME B31.3 code.
3
-
2
0
Date: J uly 8, 2003
Study Section: 2C. Hydrogen Storage
23.
Overpressure and fail

storage tank (MAWP
7,333 psig)
cold day to 6,250 psig
Heat stored gas during
day
MAWP 7,333 psig, PRV
in temp
M M Review climate conditions
in safety plan
24. Relief device failure
open
fire or explosion
Vent stack is a minimum of
15 feet above grade
L L Storage system should
contain redundant relief
devices
25. Storage tank failure Mechanical failure,
corrosion, hydrogen
embrittlement
psig
L H Storage system should
devices
26. Piping leak Mechanical failure Release of hydrogen to atm
NFPA 50A setback
distances
L H
27. Storage tank failure External fire due to
large spill of gasoline
from delivery truck
NFPA 50A requires systems
within 50 ft of aboveground
storage of flammable liquids
to prevent accumulation of
flammable liquids under the
hydrogen system. Hydrogen
system must also be at least
25 ft from the fill or vent line
on any underground
gasoline tanks
L H Design and codes should
consider stations
dispensing both hydrogen
and gasoline
Date: J uly 8, 2003
28. Piping failure Vehicle impact to
dispenser
Potential fire or explosion Bollards around dispenser L H
3
-
2
1
29. Dispenser cascade
control failure
Pressure relief device
on dispenser and
storage tanks fails
tank
vents to roof of vehicle
L H
30.
Use wrong pressure

nozzle (5,000 psig vs
3,600 psig)
vehicle fuel tank
L M
31. Drive away while
connected to
dispenser
fire or explosion
L M
32. Hose failure Mechanical failure Potential fire or explosion Hoses rated for about 8,000
psig
inspected on a regular basis
33. Leak in connection O-ring damaged or
nozzle damaged
check prior to each fill
M L
34. Vehicle pressure relief
device leaks
vents
L M
35. Fail to vent nozzle
Human error No safety hazard Venting before
disconnecting is automatic,
and is built into the nozzle
_ _
36. Vehicle tank back-
flows through
dispenser vent.
Foreign matter in
vehicle check valve
(Gas backflows when
3-way valve turned to
vent).
Potential fire or explosion Ensure careful installation of
piping to prevent introduction
of foreign material.
L M
37. Nozzle leaks after
disconnect
38. Vehicle tank isolation
valve leaks
Mechanical failure and
leaking check valve
Potential fire L M
3-22
Key Failure Modes
Table 3-6 presents how the FMEA process was categorized into the major sections of
the fueling station. Safety concerns for an electrolyzer based refueling station can arise
from the associated high-voltage electrical systems, alkali (typically KOH) leaks,
hydrogen leaks and the high-pressure systems. Further, in the system considered here,
it was assumed that the hydrogen generation and compression units are installed in a
large metal enclosure, somewhat similar in geometry to a truck-trailer container
although smaller in scale. The presence of the enclosure generates additional
complexities in terms of providing adequate ventilation and installation of flammable gas
(hydrogen) detectors. The enclosure also houses the compressor equipment.
As noted above, Table 3-6 lists the key failure modes that were considered for the
FMEA. A single failure mode may be the result of a sequence of sub-events each of
which has an associated frequency of occurrence. In such cases, the FMEA teams
relative risk rating to the failure mode occurrence frequency was the sub-event
frequency with the lowest risk rating.
Typically this sub-event would prevent other sub-events with higher risk-ratings from
materializing. For example, consider failure mode No. 9 in Table 3-6, which is an
explosion from a hydrogen leak in the enclosure due to a mechanical failure of the
equipment. While the consequence of such an explosion received a high (H) rank, the
probability of occurrence of this failure mode received an overall low (L). To prevent the
hydrogen gas from igniting, the system is designed to alarm if the hydrogen
concentration in the enclosure reaches 20 percent of the LEL, and shutdown at a
concentration of 40 percent of the LEL. In the event of a leak (with a probability of M-H),
the blower fan prevents any significant concentrations of hydrogen from accumulating.
The combination of the probability of the blower fan failing (M), the system shutdown
failing (L), and finding an ignition source (L), received an overall probability of
occurrence of low (L).
Still another example is the scenario where a fire or explosion may occur due to a
vehicle drive-away during dispensing (No. 31, Table 3-6
2
). This is a scenario that is
common to all fueling station types. The drive-away on its own was considered to be a
relatively high frequency (H) event. For ignition to occur under this failure mode, in
addition to the drive-away, the break away connection has to fail and the hose must
rupture, followed by failure of the poppet isolation valves. Finally, an ignition source
must be present. At least two of the four sub-events to drive away were assigned a low
(L) frequency of occurrence and hence the overall risk rating for the frequency of this
failure mode occurring was assigned a low (L). The frequency of occurrence for many of
the failure modes resulted in L and M designations by the FMEA team.
2
This example is repeated in each FMEA for readers who are interested in only one supply option.
3-23
Failure Modes Ranking
Table 3-7 categorizes all of the scenarios from the FMEA by combined frequency and
consequence rating in a risk binning matrix. This allows for the identification of the
Table 3-7. Risk-Binning Matrix Electrolysis Hydrogen Production,
Compressed Gas Fueling
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
High
(H)
16 0 0
Medium
(M)
10 1 0
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
3 2 0
Hydrogen Production
As noted earlier, the failure modes in this FMEA focused on events that led to the
ignition of the hydrogen gas. Potential harm could also be caused due to the electrical
power system and the alkalization system. Based on the review of existing hydrogen
equipment and the conceptual design information in Section 4, the FMEA team arrived
at the consensus that existing controls and current practices of operation resulted in a
low probability of occurrence for nearly all failure modes. As described above, a
sequence of events must occur prior to ignition, and one or more of the sub-events have
a low probability of occurrence. The highest probability of occurrence (M) was
associated with the failure of the molecular sieve dryers for the purification of the
product hydrogen (No. 11, Table 3-6); however, the FMEA team assigned the
consequence of this failure mode as low (L).
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-24
Compression Storage, Dispensing
The consequence risk rating for most failure modes was greatly influenced by the
existing controls or lack of any controls, and whether the failure mode was associated
with equipment inside or outside the enclosure. Typically, the team gave higher ratings
to failure modes that occurred inside the enclosure. The FMEA team was also
influenced by good engineering design practices in awarding risk ratings. A simple
example is the case of bollards protecting dispensing and piping equipment, which
significantly lower the frequency of catastrophic accidents from occurring.
Under the FMEA methodology being followed here, the failure mode with the highest
risk would have a risk assignment of HH (for F and C, respectively), and the lowest
would have an assignment of LL. Most failure modes received the LH designation,
which can be considered as equivalent to the MM designation. Only one failure mode
(No. 29, Table 3-6), involving the failure of the cascade dispenser control system, was
assigned MM.
Hydrogen leaks in the production and compression enclosure received H consequence
ratings (Nos. 9, 15, 17, 21, 22, Table 3-6); however, the combination of alarms and
ventilation systems resulted in L frequency ratings for all of these scenarios. The
consequences of a hydrogen ignition are higher than those in an open area, but the
active controls reduce the possibility of any leak resulting in the formation of a
flammable mixture.
The failure modes for storage and dispensing (2C and 2D) are the same as those for
liquid hydrogen (1C and 1D). The compressed gas storage capacity for the electrolyzer
system is larger than that for the liquid hydrogen or tube trailer systems because of the
requirement to continuously store hydrogen produced during the day. This increase in
storage capacity did not affect the FMEA ratings.
3.3 Steam Methane Reformer Refueling Station FMEA
The FMEA performed for a steam methane reformer (SMR) station has the following
key components:
Natural gas desulfurization unit
Steam Methane Reformer
Pure water supply unit
Purification Unit (pressure swing absorption)
Dispenser
3-25
Section 4.3 presents a detailed description of a typical SMR-based hydrogen refueling
station.
3.3.2 FMEA Results
Table 3-8 presents the results of the FMEA. The FMEA process followed the four major
areas in the fueling station. The natural gas desulfurization, steam methane reformer, and
gas clean-up (Section 3A) are unique among the supply options in this report. Natural gas
and steam are reacted in the reformer at 10 atm. The product gas is processed by the
PSA and the pure hydrogen is fed into a compressor. The 10 atm steam reformer
assumed in this study presents different safety challenges than an atmospheric system.
All components of this SMR-based station except the dispenser are located in a ventilated
enclosure. This strategy eliminates the requirement for some classified electrical
equipment. A similar strategy was assumed for the electrolyzer system. The storage and
dispensing equipment is similar to the other fuel supply options.
SMR and compressor located in a ventilated enclosure with hydrogen detectors
Only trained personnel have access to the fuel production and compressor
enclosure. Public access to the storage equipment is also prohibited.
equipment)
Key Failure Modes
Table 3-8 categorizes all of scenarios from the FMEA by combined frequency and
consequence rating. This risk binning allows for the identification of the prioritization of
safety improvement efforts for the fueling system. Table 3-8 presents how the FMEA
process was categorized into the major functions (supply, compression, storage, and
delivery) required in a hydrogen fuel station. Broadly stated, the safety concerns for the
steam methane reformer based hydrogen supply system can arise from the high
pressure reactor, the PSA system, hydrogen leaks, and the proximity of ignition sources
(SMR burners).
3
-
2
6
Table 3-8. SMR Station FMEA Results
Process: 3. SMR
Study Section: 3A. Natural Gas Steam Reforming, Hydrogen Purification
Design Intent: Generate 1.25 kg/h of >99.99% hydrogen at 150 psig from reforming of natural gas
1. Natural gas line leak
downstream of
compressor
Mechanical failure Potential fire/explosion Combustible gas detector
inside enclosure and
enclosure is ventilated
L H
2. Natural gas
compressor high
discharge pressure
Instrument failure,
pressure relief valve
(PRV) fails to open
(set at 150 psig)
Overpressure reformer
(design pressure 150 psig)
vented to atmospheric stack
downstream, also pressure
relief valve and rupture disc
on reformer
L H
3. Desulfurizer failure Media is saturated or
deactivated
Unable to remove odorant or
hydrogen sulfide, poison
reformer and shift catalyst
and unable to make sufficient
hydrogen, increase in purge
gas flow to reformer and
potential high temperature
on reformer
L H Provide odorant detector
downstream of desulfurizer
4. Desulfurizer failure High level of
mercaptans or high
natural gas flow
Unable to remove heat of
adsorption and potential fire
in carbon bed
L H Include heat release
analysis from sulfur remova
equipment in design review
5. Deionized water pump
failure
Mechanical failure No steam for reforming of
natural gas, coke reformer
tubes, potential tube failure
Low water flow and high
temperature shutdowns
L M
6. Water quality failure Deionization system
failure
Plug heat exchanger tubes,
potential tube failure
Conductivity analyzer L L
7. Air blower failure Mechanical failure Loss of flame and potential
explosion
Flame safety shutdown on
loss of flame and low
temperature requires purge
before restart
L H
3
-
2
7
8. Natural gas feed valve
leaks
Mechanical failure Potential explosion in
reformer on light-off
Mandatory purge before
light-off
L H
9. Reformer flame failure Natural gas pressure
swing or condensate
Potential explosion in
reformer upon re-ignition
Flame safety shutdown on
loss of flame and low
temperature requires purge
before restart
L H
10. Reformer temperature
or combustion control
failure
Instrument failure
causes ratio of natural
gas to steam to be too
high
Damage tubes, reformer
catalyst, exceed CO/CO
2
capacity of PSA unit
on reformer
L H
11.
Overpressure reformer
(design pressure 150
psig)
PSA feed control
valve closed
Fail reformer tube Pressure relief device
vented to atmospheric stack
downstream, also pressure
relief valve and rupture disc
on reformer
L H
12. Waste heat recovery
water exchanger
failure
Mechanical failure Water spills into exhaust
stack
No safety hazard
_ _
13. Waste heat recovery
natural gas exchanger
failure
Mechanical failure Natural gas leaks into
exhaust stack and ignites
High stack temperature and
CO shutdown
L M
14. Hydrogen gas leak
into enclosure
process gas cooler,
valves and other
potential leak points
Process gas flow into
enclosure, potential fire or
explosion
Combustible gas detector
L H
15. Condensate separator
control valve fails open
Mechanical failure Process gas into condensate
disposal system and potential
fire or explosion
Condensate is recycled
M M Condensate surge tank ven
should be vented to stack
16. Condensate separator
control valve fails
closed
Instrument failure Slug of condensate in the
hydrogen feed to PSA unit
Product quality issue
No safety hazard
Water traps in line to PSA
unit
_ _
3
-
2
8
17. Shift reactor failure Hot spot due to
methanation reaction
Release of process gas Combustible gas detector
L H
18. PSA unit failure Adsorbent failure due
to age
Unable to purify hydrogen
and damage vehicle fuel cell
No safety hazard
_ _ Verify if product gas from
PSA unit is analyzed
19. PSA control failure
during regen
Leak hydrogen to
reformer
Increase temperature in
reformer
High temperature shutdown L H
20. Leak in PSA waste
gas line
Mechanical failure Release of CO and hydrogen,
potential toxic exposure to
CO and potential fire or
explosion
CO monitor in enclosure
exhaust
L M
Process: 3. SMR
Design Intent: Compress 1.25 kg/h of hydrogen from 150 psig to 6,250 psig
21.
Compressor suction
line failure
line or fitting
ASME B31.3 code
300F
No safety hazard
_ _
23.
Lubrication system
failure
L H
24.

diaphragm compressor
L H
3
-
2
9
fails open
Mechanical failure Relief valves are vented back
to ballast or blow down tank
No safety hazard
_ _
27. Valve on discharge of
compressor fails
closed
human error and
failure of pressure
explosion
L H
28. High pressure (6,250
line failure
L H
Process: 3. SMR
29.

Heat stored gas
during day
in temp
in safety plan
open
fire or explosion
15 feet above grade
L L
corrosion, hydrogen
embrittlement
psig
devices
NFPA 50A setback
distances
L H
3
-
3
0
from delivery truck
on any underground
gasoline tanks
consider stations
and gasoline
Process: 3. SMR
dispenser
control failure
on dispenser and
storage tanks fails
tank
vents.
L H
36.
Use wrong pressure

nozzle (5,000 psig vs.
3,600 psig)
vehicle fuel tank
L M
connected to
dispenser
fire or explosion
L M
psig
nozzle damaged
M L
device leaks
vents
L M
3
-
3
1
_ _
flows through
dispenser vent.
Foreign matter in
vehicle check valve
(Gas backflows when
vent).
L M
disconnect
valve leaks
Mechanical failure Potential fire or explosion L M
3-32
Table 3-8 lists the key failure modes that were considered for the FMEA. A single failure
mode may be the result of a sequence of sub-events, each of which has an associated
frequency of occurrence. In such cases, the relative risk rating that was assigned by the
FMEA team to the failure mode occurrence frequency was the sub-event frequency with
the lowest risk rating. Typically, this sub-event would prevent other sub-events with
higher risk-ratings from materializing. For example, consider failure mode No. 9 in Table
3-8, which is an explosion that results from relighting the reformer after a flame-out.
While the probability of flame failure occurrence is high (H), the overall frequency of an
explosion occurring received an L ranking as the flame safety shutdown procedure on
loss of flame and low temperature requires purge before restart.
Failure Modes Ranking
Table 3-9 categorizes all scenarios from the FMEA by combined frequency and
consequence rating in the risk binning matrix. This allows for the identification of the
Table 3-9. Risk-Binning Matrix SMR Hydrogen Production, Compressed
Gas Fueling
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
High
(H)
22 0 0
Medium
(M)
10 2 0
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
2 1 0
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-33
Hydrogen Production
As seen in the risk binning matrix in Table 3-9, 24 (55 percent) of the failure modes
present a moderate risk. As noted previously, the FMEA team took into consideration
good engineering design as well as practices. In the hydrogen production and
purification system, the item with highest risk received a ranking of MM and involved the
improper venting of a surge tank in the hydrogen process line (No. 15, Table 3-8). The
FMEA team also identified that this failure mode could be mitigated with some minor
design changes.
The results for this section are similar to other fueling stations and are repeated for
completeness. MM ratings were also assigned to scenarios in the fuel storage and
vehicle dispensing sections of the fueling station. These scenarios apply to all of the fuel
supply options. Both of these scenarios relate to an over pressure of the fuel tank and
subsequent release of hydrogen from the pressure relief valve or vehicle pressure relief
device. Under unusual weather conditions, the fueling station storage tanks can be filled
while very cold and then heated during the day. The range in ambient temperature
swings is taken into account in fueling station design; however, unusual temperature
variations are possible. A failure in the instrumentation associated with the temperature
compensation system could result in the overpressure of a vehicle tank during fueling.
The consequence ratings for the hydrogen compression system were all M or lower. For
the liquid hydrogen system, the compressor is in the open and leaks would not have an
opportunity to accumulate.
existing controls or lack of any controls. For example, in the cases where a hydrogen
leak detector was present as a control, the resulting consequence risk level was
mitigated to either an M or an L from an almost certain H in the absence of the control.
The FMEA team observed that engineering design equipment, system or
civil/architectural design played an important role in the associated risk level. A
simple example is the case of bollards protecting dispensing and piping equipment,
which significantly lowers the frequency of catastrophic accidents from occurring.
have had an H-rating but were reduced by associated lower risk sub-events. A single
failure mode may be the result of a sequence of sub-events each of which has an
event frequency with the lowest risk rating. Typically this sub-event would prevent other
sub-events with higher risk-ratings from materializing. For example, consider the
scenario where a fire or an explosion may occur due to a vehicle drive-away during
3-34
dispensing (Item No. 37, Table 3-8)
3
. This scenario is unavoidable in all fueling station
types because of the potential for human error. The drive-away on its own was
considered to be a relatively high frequency (H) event. However, for ignition to occur
under this failure mode, in addition to the drive-away, the break away connection has to
fail and the hose must rupture, followed by failure of the poppet isolation valves. Finally,
an ignition source must be present. At least two of the four sub-events to drive away
were assigned a low (L) frequency of occurrence, and hence the overall risk rating for
the frequency of this failure mode occurring was assigned a low (L). The frequency of
occurrence for many of the failure modes resulted with L and M designations by the
FMEA team.
3.4 Tube Trailer Compressed Hydrogen Refueling Station
FMEA
The tube trailer based compressed hydrogen refueling station for which an FMEA was
performed has the following key components:
Nominally 210 atm (3,100 psig) hydrogen gas tube trailer storage
Dispenser
3.4.2 FMEA Results
Table 3-10 presents the results of the FMEA. The FMEA process followed the major
functions (supply, compression, storage, and delivery) required in a hydrogen fueling
station. The features unique to the tube trailer station are the tube trailer storage and
transfer of tubes by the hydrogen supplier. The high-pressure compression, storage,
and dispensing equipment are similar for the other fuel supply options.
Tube trailer transfer and storage
Only trained personnel have access to the fuel transfer equipment. Public access to
the storage equipment is also prohibited.
3
3
-
3
5
Table 3-10. Tube Trailer Hydrogen Station FMEA Results
Process: 4. Compressed Hydrogen
Study Section: 4A. Hydrogen Tube Trailer Delivery
Design Intent: Unload and store 343 kg of hydrogen at 3,130 psig from a tube trailer
1. Compressed trailer
leak
Mechanical failure
due to road vibration
Potential fire Unloading inspection by
station rep or driver
Hydrogen leak detectors in
area
M L
leak
Vehicle impact to
trailer while at
unloading spot
damages hydrogen
piping
Potential fire/explosion Tube trailer parked behind
fence
L M Need additional staging
area to replace tube trailer
leak
Vehicle impact to
trailer while in staging
area damages
hydrogen piping
Potential fire/explosion Driver puts caution cones
around truck
M M Establish separation
distance of vehicles from
unloading truck
leak
Trailer impacts bollard
or other structure
during change out
Potential fire/explosion Driver training M M Need sufficient staging area
to promote safe changeout
of trailers
5. Hose connection leaks
during detachment or
attachment
improper connection,
improper venting
before disconnect or
leak when making
new connection
Potential fire Unloading is continuously
monitored by both driver and
station rep.
Driver training and unloading
checklist, using standard
unloading hydrogen
M L Implement a leak check
when making connection to
new trailer
3
-
3
6
6. Tube trailer failure External fire due to
from delivery truck
Potential failure of tank due
to overheating of metal
on any underground gasoline
tanks
consider stations
and gasoline
7. Failure of pressure
relief device open
Mechanical failure Release of hydrogen to
atmosphere and potential
fire or explosion
Relief devices are vented
through a stack on the trailer
M L
8. Failure of tube on
trailer
Mechanical failure Release of hydrogen to
atmosphere and potential
fire or explosion
L H
Process: 4. Compressed hydrogen
Design Intent: Compress 1.25 kg/h of hydrogen from 200 psig to 6,250 psig
9. Pressure reducing
valve fails open
Mechanical failure Overpressure compressor
or downstream piping and
release of hydrogen and
potential fire and projectiles
High and low pressure limit
switch on compressor
Pressure relief valve on
compressor discharge
L H
10.
Compressor suction
line failure
line or fitting
potential fire
L M Piping in the entire system
ASME B31.3 code
300F
No safety hazard
_ _
12.
Lubrication system
failure
potential fire
L M
3
-
3
7
13.

potential fire
compressor
L M
fails open
Mechanical failure Relief valves are vented to
vent stack
No safety hazard
_ _
16.
Valve on discharge of
compressor fails
closed
human error and
failure of pressure
hydrogen and potential fire
or explosion
L M
17.
High pressure (6,250

line failure
L M
Process: 4. Compressed Hydrogen Tube Trailer
18. Fill storage tank on
Heat stored gas
during day
in temp
in safety plan
open
fire or explosion
15 feet above grade
devices
corrosion, hydrogen
embrittlement
and potential fire or
explosion
psig
devices
and potential fire or
explosion
NFPA 50A setback distances L H
3
-
3
8
from delivery truck
Potential failure of tank due
to overheating of metal
on any underground gasoline
tanks
consider stations
and gasoline
Process: 4. Compressed Hydrogen
dispenser
control failure
on dispenser and
storage tanks fails
tank
L H
25.
Use wrong pressure

nozzle (5,000 psig vs
3,600 psig)
vehicle fuel tank
L M
connected to
dispenser
fire or explosion
L M
psig
nozzle damaged
M L
device leaks
L M
3
-
3
9
Human error No safety hazard Venting before disconnecting
is automatic, and is built into
the nozzle
_ _
flows through
dispenser vent.
Foreign matter in
vehicle check valve
(Gas backflows when
vent).
M
disconnect
valve leaks
Mechanical failure
and leaking check
valve
Potential fire L M
dispenser
control failure
Instrument failure Overpressure vehicle fuel
tank
M M Limit maximum possible
exposure of the vehicle tank
to 1.25 x MAWP through
appropriate piping of the
cascade system. Install
pressure relief device on
dispenser to protect against
vehicle overpressure.
3-40
equipment)
Key Failure Modes
Table 3-10 presents how the FMEA process was categorized into the major functions
(supply, compression, storage, and delivery) required in a hydrogen fueling station.
Broadly stated, safety concerns for the tube trailer station stem from possible hydrogen
leaks and the high-pressure system. As noted above, Table 3-10 lists the key failure
modes that were considered for the FMEA. As in the case of other types of hydrogen
fueling stations, a single failure mode may be the result of a sequence of sub-events,
each of which has an associated frequency of occurrence.
In such cases, the relative risk rating assigned by the FMEA team to the failure mode
occurrence frequency was the sub-event frequency with the lowest risk rating. Typically,
this sub-event would prevent other sub-events with higher risk-ratings from
materializing. For example, consider failure mode No. 6 in Table 3-10, which is an
explosion from the potential failure of the tubes due to a large gasoline spill in the
vicinity. While the consequence of such an explosion received a high (H) rank, the
probability of occurrence of this failure mode received an overall low (L) rank. To
prevent the explosion from occurring, the tubes will be vented using pressure relief
devices in the event of an over pressure. Further, code-related set back distances for
equipment placement and fuel transfer mitigated some of the H level risks to L level.
Table 3-11 categorizes all of scenarios from the FMEA by combined frequency and
consequence rating. This risk binning allows for the overall identification of the
Hydrogen Delivery and Storage
The highest risk levels assigned by the FMEA team was MM to failure modes number 3
and 4 in Table 3-10. Both result from a fracturing impact to the tube trailer. The FMEA
team also identified further steps that would mitigate this risk to lower levels. The
mitigation steps included establishing adequate separation distances and staging areas
for tube transfer that would minimize accidental vehicle/trailer impact.
Several scenarios received LM ratings. Table 3-10 indicates recommendations for
improving the risk ratings.
3-41
Table 3-11. Risk-Binning Matrix Tube Trailer Delivery, Compressed Gas
Fueling
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
High
(H)
9 0 0
Medium
(M)
13 4 0
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
1 4 0
High pressure compression, storage, and dispensing is similar in design and function to
the other fueling stations considered here. MM ratings were also assigned to scenarios
in the fuel storage and vehicle dispensing sections of the fueling station. These
scenarios apply to all of the fuel supply options. Both scenarios relate to an over
pressure of the fuel tank and subsequent release of hydrogen from the pressure relief
valve or vehicle pressure relief device. Under unusual weather conditions, the fueling
station storage tanks can be filled while cold and then heated throughout the day. The
range in ambient temperature swings is taken into account in fueling station design;
however, unusual temperature variations are possible. A failure in the instrumentation
associated with the temperature compensation system could result in the overpressure
of a vehicle tank during fueling.
existing controls or lack of any controls. For example, in the cases where a hydrogen
leak detector was present as a control, the resulting consequence risk level was
mitigated to either an M or an L from an almost certain H in the absence of the control.
The FMEA team observed that engineering design equipment, system or
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-42
civil/architectural design played an important role in the associated risk level. A
simple example is bollards protecting dispensing and piping equipment, which
significantly lower the frequency of catastrophic accidents from occurring.
Many top-level occurrences are a product of sub-events that individually may have an
H-rating but were reduced by associated lower risk sub-events. A single failure mode
may be the result of a sequence of sub-events, each of which has an associated
frequency of occurrence. In such cases, the relative risk rating that was assigned by the
FMEA team to the failure mode occurrence frequency was the sub-event frequency with
the lowest risk rating. Typically this sub-event would prevent other sub-events with
higher risk-ratings from materializing. For example, consider the scenario where a fire or
explosion may occur due to a vehicle drive-away during dispensing (No. 27, Table 3-
10
4
). This scenario is unavoidable in all fueling station types because of the potential for
human error.
The drive-away on its own was considered to be a relatively high frequency (H) event;
however, for ignition to occur under this failure mode, in addition to the drive-away the
break away connection has to fail and the hose must rupture, followed by failure of the
poppet isolation valves. Finally, an ignition source must be present. At least two of the
four sub-events to drive away were assigned a low (L) frequency of occurrence and
hence the overall risk rating for the frequency of this failure mode occurring was
assigned low (L). The FMEA team designated L and M as the frequency of occurrence
for many of the failure modes.
3.5 CNG Refueling Station FMEA
The compressed natural gas (CNG) refueling station for which an FMEA was performed
has the following key components
Dispenser
Section 4.5 presents a detailed description of a typical CNG-based refueling station.
4
3-43
3.5.2 FMEA Results
Table 3-12 presents the results of the FMEA. The FMEA process followed the four
major areas in the fueling station. The typical CNG station is supplied natural gas
directly by the city-gas lines and this is where it differs from the hydrogen stations
described previously. Once the station receives the fuel, the remaining major steps such
as high pressure compression, storage, and dispensing are in concept similar to the
hydrogen refueling stations described earlier.
Natural gas delivery
Site layout and equipment meets NFPA 52
Public access to the compression and storage equipment is also prohibited.
equipment)
Key Failure Modes
Table 3-12 presents how the FMEA process was categorized into the major functions
(supply, compression, storage, and delivery) required in a fueling station. Broadly
stated, safety concerns for a CNG station stem from natural gas leaks and associated
high-pressure systems. As noted above, Table 3-12 lists the key failure modes that
were considered for the FMEA. As in the case of the other types of fueling stations
presented in this report, a single failure mode may be the result of a sequence of sub-
events each of which has an associated frequency of occurrence. In such cases, the
relative risk rating that was assigned by the FMEA team to the failure mode occurrence
frequency was the sub-event frequency with the lowest risk rating. Typically this sub-
event would prevent other sub-events with higher risk-ratings from materializing. For
example, consider failure mode No. 6 in Table 3-12, which is an explosion or fire from
the potential failure of the compressor seals. While the consequence of such an
explosion received a high (H) rank, the frequency of occurrence of this failure mode
received an overall low (L). Even if the frequency of a seal failure is higher than L, the
failure mode in No. 6 is mitigated by the frequency of an ignition occurring, since both a
failure of the detectors as well as presence of an ignition source must occur.
Table 3-13 categorizes all 26 scenarios from the FMEA by combined frequency and
consequence rating. This risk binning allows for the overall identification of the
3
-
4
4
Table 3-12. CNG Station FMEA Results
Process: 5. CNG
Study Section: 5A. Natural gas delivery
Design Intent: Receive and dry pipeline natural gas at 6810 SCFD
1. Natural gas line leak Mechanical failure Potential fire/explosion Gas is odorized
Combustible gas detectors
L H
2.
Natural gas dryer

failure
Adsorbent saturated Unable to remove moisture
from gas and potential icing
in vehicle
Corrosion and/or leakage in
vehicle
L L
Process: 5. CNG
Study Section: 5B. Natural Gas Compression
Design Intent: Compress natural gas from 20 psig to 4,000 psig
3. Compressor suction
line failure
line or fitting
PRV. Release of natural gas
Gas is odorized
L M Piping in the entire system
ASME B31.3 code
4. Cooling system
failure
Loss of cooling fluid Reduce piston life
No safety hazard
_ _
5. Lubrication system
failure
Loss of fluid Release of natural gas and
Gas is odorized
L M
6. Seal failure Mechanical failure Release of natural gas and
Gas is odorized
L M
7. Compressor suction
or discharge valve
failure
3
-
4
5
8. Pressure relief
device fails open
Mechanical failure Relief valves are vented to a
stack
No safety hazard
_ _
9. Valve on discharge
of compressor fails
closed
Mechanical failure
or human error and
failure of pressure
natural gas and potential fire
or explosion
Gas is odorized
L M
10. High pressure
(4,000 psig) natural
gas supply line
failure
Mechanical failure Release of natural gas and
Gas is odorized
L M
Process: 5. CNG
Study Section: 5C. Natural Gas Storage
Design Intent: Store compressed natural gas at 4,500 psig
11.
Overpressure and
failure storage tank
(MAWP 4,000 psig)
cold day to 4,500
psig
Heat stored gas
during day
Release of natural gas and
thermal expansion is
approximately 5,200 psig
based on 50C increase in
temp
in safety plan
12.
Relief device failure

open
Mechanical failure Release of natural gas and
Relief devices vent to stack
Gas is odorized
devices
corrosion,
Release of natural gas and
psig
devices
14. Piping leak Mechanical failure Release of natural gas and
NFPA 52 setback distances
Gas is odorized
L H
large spill of
gasoline from
delivery truck
NFPA 52 setback distances
Gas is odorized
consider stations
dispensing both CNG and
gasoline
3
-
4
6
Process: 5. CNG
Study Section: 5D. CNG Dispensing
Design Intent: Dispense 680 SCF per vehicle at 3,000 or 3,600 psig
dispenser
17.
Dispenser cascade
control failure
Pressure relief
device on dispenser
and storage tanks
fails
tank
vents
CNG filling uses different
heat of compression
compensation than
hydrogen
L H
18.
Use wrong pressure

nozzle (3,600 psig
vs 3,000 psig)
vehicle fuel tank
L M In CNG service older
vehicles have a variety of
different type fittings
connected to
dispenser
fire or explosion
L M
20. Hose failure Mechanical failure Potential fire or explosion Hoses rated for CNG service L M Should be tested or
nozzle damaged
M L
22. Vehicle pressure
relief device leaks
vents
L M
_ _
flows through
dispenser vent.
Foreign matter in
vehicle check valve
(Gas back flows
when 3-way valve
turned to vent).
L M
3
-
4
7
disconnect
26. Vehicle tank
isolation valve leaks
Mechanical failure Potential fire or explosion L M
3-48
Table 3-13. Risk-Binning Matrix CNG, Compressed Gas Fueling
Frequency (F)
Low
(L)
Medium
(M)
High
(H)
Combined Risk:
Consequence x
Frequency
High
(H)
6 0 0
Medium
(M)
12 1 0
C
o
n
s
e
q
u
e
n
c
e

(
C
)
Low (L) or
Negligible
(-)
2 1 0
The highest risk levels assigned by the FMEA team were MM to failure modes, giving
them a moderate risk status per the risk binning matrix. However, 10 additional failure
modes that received the LH rating are also categorized into the moderate risk bins. In
many cases, the FMEA team identified steps that would mitigate the moderate risks to
lower levels.
Delivery of NG is a very common procedure and the FMEA team did not identify any
unique risks associated with this process. High pressure compression, storage, and
dispensing are conceptually similar in design and function to the other fueling stations
considered here.
MM ratings were also assigned to scenarios in the fuel storage and vehicle dispensing
sections of the fueling station. These scenarios apply to all of the fuel supply options.
Both of these scenarios relate to an over pressure of the fuel tank and subsequent
release of methane from the pressure relief valve or vehicle pressure relief device. The
range in ambient temperature swings is taken into account in fueling station design;
however, unusual temperature variations are possible. A failure in the instrumentation
associated with the temperature compensation system could result in the overpressure
of a vehicle tank during fueling.
High Risk
Low or
Negligible
Risk
Moderate
Risk
3-49
existing controls or lack of any controls. For example, in the cases where a NG leak
detector was present as a control, the resulting consequence risk level was mitigated to
either an M or an L from an almost certain H in the absence of the control. The FMEA
team observed that engineering design equipment, system or civil/architectural
design played an important role in the associated risk level. A simple example is the
case of bollards protecting dispensing and piping equipment, which significantly lower
the frequency of catastrophic accidents from occurring.
have had an H-rating but were undermined by associated lower risk sub-events. A
single failure mode may be the result of a sequence of sub-events each of which has an
event frequency with the lowest risk rating. Typically this sub-event would prevent other
sub-events with higher risk-ratings from materializing. For example, consider the
scenario where a fire or explosion may occur due to a vehicle drive-away during
dispensing (No. 19, Table 3-10)
5
. This scenario is unavoidable in all fueling station
types because of the potential for human error.
The drive-away on its own was considered to be a relatively high frequency (H) event.
However, for ignition to occur under this failure mode, in addition to the drive-away the
break away connection has to fail and the hose must rupture, followed by failure of the
poppet isolation valves and finally an ignition source must be present. At least two of the
four sub-events to drive away were assigned a low (L) frequency of occurrence and
hence the overall risk rating for the frequency of this failure mode occurring was
assigned a low (L). The frequency of occurrence for many of the failure modes resulted
with L and M designations by the FMEA team.
5
4-1
4. FUELING STATION DOCUMENTATION
FMEA INPUTS
4.1 Liquid Hydrogen Documentation
Liquid Hydrogen Delivery
A cryogenic tank truck delivers liquid hydrogen to the fueling station, which transfers the
liquid to the station tank. Because of its much higher density (as discussed in Section
5), considerably more hydrogen is transported as a cryogenic liquid in tank trucks than
as a compressed gas in tube trailers. The delivered liquid is maintained at temperatures
below -250C (420F) in one or more vacuum-jacked vessels at the station.
In this station design, the liquid is warmed in a heat exchanger. The vapor from boil-off
or warmed liquid is compressed into high-pressure gas storage vessels that supply the
dispensers. This approach was selected because of the design basis for the fueling
station. Alternatively, for stations with a throughput high enough that boil-off vapor is
negligible, the liquid can be pumped to high pressure and then vaporized. This reduces
costs by eliminating the multi-stage compressor and its substantial drive power
requirements. Figure 4-1 illustrates the pressure-enthalpy pathway for converting liquid
hydrogen to compressed gas. Both vaporizer/compressor and cryogenic pump
pathways are indicated.
One disadvantage of liquid hydrogen delivery is the potential for boil-off as heat enters
the cryogenic storage tank. Some boil-off loss inevitably occurs at various points in the
infrastructure chain. This boil-off loss can be negligible for fuel stations with a high
throughput, but it can be substantial for low-throughput stations (e.g., where liquid
hydrogen deliveries are less frequent than once per week). Additional consideration of
boil-off losses is included in subsequent discussions of fueling station design and
components.
The broken-line curve in Figure 4-1 is the hydrogen saturation dome. Hydrogen is a
liquid to the left of this dome, a vapor to the right, and a liquid-vapor mixture within the
dome. Hydrogens critical point is at the peak of the dome, and hydrogen above this
point is said to be supercritical.
The vaporize-and-compress option starts with the horizontal line extending to the right
from the liquid side of the dome in Figure 4-1. This line denotes vaporization of the
liquid hydrogen (from the left to the right side of the dome) followed by warming of the
hydrogen gas to ambient temperature. Vaporizer is technically a misnomer, since
substantially more heat transfer is needed to warm the gas than to vaporize the liquid.
In Figure 4-1s example, the ambient-temperature of 70F hydrogen is assumed to be
compressed to 5,000 psi in a four-stage compressor with intercooling after each stage.
4-2
10
100
1,000
10,000
-500 0 500 1,000 1,500 2,000 2,500 3,000
Enthalpy ( Btu / Lbm )
P
r
e
s
s
u
r
e

(

p
s
i
a

)
Saturated
liquid
hydrogen at
60psig
Hydrogen saturation line
Compressed hydrogen at 5,000 psig & 60
o
F
Vaporization & compression
Pumping &
warming
Ideal pumping power
=199 Btu/Lbm
=10 hp per kg/min
4-stage compressor with
intercooling,
ideal drive power
=2,628 Btu/Lbm
=137 hp per kg/min
Figure 4-1. Pressure versus Enthalpy for Equilibrium Hydrogen,
Illustrating Two Alternative Paths for Dispensing Compressed
Hydrogen from Stored Liquid Hydrogen
The advantage of the vaporize-and-compress strategy is that it produces less boil-off
vapor and it can process some or all of the vapor that must be vented if a pump is
used.
6
The liquid hydrogen storage tank is obviously a key component. A 12,000-gallon tank
was analyzed for this vehicle fueling application. With a vehicle fueling rate of 10 cars
per day, the tank could be managed to avoid boil off and venting of hydrogen. While
venting hydrogen vapor from the tank does not pose a safety risk, it is desirable to use
the product for vehicle fueling. Figure 4-2 illustrates how the tank pressure would vary if
fuel were drawn either from the vapor or liquid space. A combination of 38 percent of
the fuel drawn from the vapor space with the balance from the liquid would maintain a
constant pressure in the liquid tank and eliminate the need for venting. The calculations
that demonstrate the thermal management of the liquid hydrogen verified that the
component sizing of the fueling station was appropriate for a 10 vehicle per day
demand.
6
An exception is the previously mentioned cryogenic pump-compressor combinations that can process
liquid and vapor mixtures.
4-3
0
20
40
60
80
100
120
0 2 4 6 8 10 12 14 16 18 20
Time ( days )
T
a
n
k

P
r
e
s
s
u
r
e

(

p
s
i
g

)
Ifvapor is fed to vaporizer and compressor
If liquid is fed to vaporizer
and compressor
If62% bymass liquid and 38% by mass
vapor is fed to vaporizer and compressor
Tank refilled
with 3,000
gallons of
10 psig
Sat.liquid
every 17.3
days
4,500-gallon LH2 tank,
1%/dayNER,
150-psig PRV,
ullage adequate to avoid liquid-full condition,
30 kg/dayaverage consumption rate
Figure 4-2. Illustration of Liquid Hydrogen Storage Tank Saturation Pressure
Variation: Pressure Changes for Noted Conditions for
Withdrawal of Liquid, Vapor, or Liquid-vapor Mixture
All cryogenic hydrogen tanks of this type are of vacuum-jacketed construction. The
inner tank is typically stainless steel designed and tested in a manner consistent with
the ASME pressure vessel code. The outer tank or jacket is typically carbon steel. The
interstitial vacuum space is filled with a low-conductivity granular material such as
Perlite or multi-layer insulation (MLI) to minimize both radiation and convection heat
transfer. The inner tank has various pressure-relief devices consistent with applicable
codes. This includes pressure-relief valves backed up by rupture disks, which open to
vent product to preclude over-pressuring the inner tank. There are usually two sets of
these valve/disk combinations so that one set can be isolated (e.g., for valve testing or
disk replacement). The outer vessel is not a pressure vessel, and therefore it is fitted
with a relief device so that it vents if the inner tank leaks into the vacuum space. Two
important specifications (in addition to capacity) affecting liquid hydrogen tanks are the
maximum allowable working pressure (MAWP) and normal evaporation rate (NER).
7
7
NER is usually expressed as a percent of the tank capacity that evaporates per day due to heat leaks. It
is important to note if the NER is specified in terms of a gas other than hydrogen and the vent pressure
associated with the NER specification.
4-4
The hydrogen liquid and vapor phases in the storage tank are generally at or near
saturation (i.e., equilibrium), and both the saturation pressure and temperature increase
with time, if there is no venting, as heat leaks into the tank. The saturation pressure and
temperature of the hydrogen delivered by the tank truck is relatively low because it is
fresh from the liquefier. There are two possible strategies for using cryogenic liquid
hydrogen tanks in a fueling station application. One option is to equip the tank with a
pressure-regulator valve so that it vents to maintain a constant pressure less than the
MAWP. The other option is to allow the tank pressure to increase from the relatively low
level following tank-truck delivery up to the PRD setting. If the station throughput is high
enough and the delivery of fresh cold liquid hydrogen is frequent enough, then the
storage tank pressure will never reach the PRD setting and no product will be lost due
to venting.
Similar to the other fuel supply options, the fuel station components reflect sizing for
fueling 10 vehicles per day. A gas compressor was sized to operate six hours a day to
fuel 10 vehicles. Consequently, the fueling station could handle a larger vehicle fueling
rate. The larger compressor capacity reduces the requirement for on-site storage
compared with on-site production options.
Table 4-1 summarizes the liquid hydrogen equipment and product specifications.
Table 4-2 is a summary of the codes and standards applicable to liquid hydrogen
storage. Figures 4-3 through 4-5 show representative process flow diagrams (PFD),
piping and instrument diagrams (P&ID), and site layout plan.
Table 4-1. Liquid Hydrogen Equipment and Product Specification
Item Specification
Cryogenic Delivery Truck 12,000 gal
Cryogenic Liquid Hydrogen Storage Tank 5,000 gallon capacity
Vaporizer/Heat Exchanger 5 kg/hr flow rate
Hydrogen Compressor Compress to 6,250 psi
4 kg/h nominal Class I, Division 1,
Group B Service
Explosion proof equipment in open
area
Compressed Hydrogen Storage Vessels 39 kg H
2
capacity
1.1 WC m
3
H
2
capacity at 6,250 psi
Compressed Hydrogen Dispenser Fueling at 5,000 and 3,600 psi
Sherex nozzles with three-way valve
Break-away coupling of nozzle
4
-
5
STORAGE
DISPENSER
2
4
5
1
3
6
Composition T P
H2
kg/h
1 Liquid Hydrogen from Delivery Truck (gal) ~5,000 -253 1
2 Liquid Hydrogen to Compressed Storage 3.70 -250 3
3 Liquid Hydrogen to Vapor-Phase 3.70 10 3
4 High-Pressure Compressed Hydrogen 3.70 40 425
5 High-Pressure Compressed Hydrogen Storage 20 425
6 Hydrogen Dispenser 30 20 340
atm Stream # Description
o
C
LH
2
TANK
Figure 4-3. Process Flow Diagram for Liquid Hydrogen Refueling
4
-
6
Liquid
Vapor
Property of:
TIAX LLC
1061 De Anza Blvd.
Cupertino, CA 95014
PROPRIETARY INFORMATION
Piping and Instrumentation Diagram
Hydrogen Fueling Station - Liquid Hydrogen
Delivery
SIZE DWGBY DWG NO REV
B
Charles Powars/
J ohn Woody
D130-P-1001 1a
SCALE Notto Scale 07/23/03 SHEET 1 OF 1
PI
TI
PI
LI
LIQUID
HYDROGEN
DELIVERY
HYDROGEN TO
VENT
A
A
HYDROGEN TO
DISPENSER
A
OPI
SA
4 TO 6 STAGE
COMPRESSION
PRESSURE-BUILD
CIRCUIT (TOMAINTAIN
MINIMUM COMPRESSOR
SUCTION PRESSURE
NATURAL OR FORCED
DRAFT HEAT
EXCHANGER
Level Indicator
Conductivity Indicator
Oxygen Indicator
Temperature Indicator
LI
CI
TI
O
2
I
Pressure Indicator PI
Hydrogen Indicator H
2
I
DP Dew Point Analyser
Oil Pressure Indicator OPI
SA Seal Failure Alarm
Pressure Relief Valve
Rupture Disk
Hydrostatic Relief Valve
A A
Figure 4-4. Piping and Instrumentation Diagram for Liquid Hydrogen Refueling
4-7
Table 4-2. Codes and Standards Regarding Compressed and Liquid Hydrogen
Storage
Distance from Gaseous Hydrogen
Storage
Distance from Liquid
Hydrogen
Element of Station NFPA 50A
IFGC
704.2
IFC
2209.3.1.1 NFPA 50B
IFC
2206.3.1.2
Walls with minimum fire rating 5 ft (2 hour) 5 ft. (3-hour)
Wall openings (doors & windows) 25 ft 75 ft.
Intake vents 50 ft 75 ft
Lot Line 5 ft 10 ft 15 ft 25 ft
Places of public assembly 50 ft 75 ft
Parked vehicles 15 ft 25 ft
Gasoline Storage 50 ft 50 ft
Overhead Electric Wire 5 ft 0 ft 3 ft
Cement Block Wall 0 ft 0 ft 5 ft 15 ft
Public sidewalks 15 ft 10 ft 15 ft 25 ft -
Overhead Trolley Bus Wire 50 ft
Office/Store
Building having noncombustible
wall surfaces that are not part of a
1 hour fire resistant-rated
assembly
25 ft
Ignition Source 25-50 ft
0 ft w/2-hour
wall
10 ft 25 ft 50 ft
Gasoline and Hydrogen
Dispensing
10 ft 15 ft
Office/Store 10 ft 15 ft
HVAC, doors, and windows 15 ft
4
-
8
Security Fence
Fuel Station Perimeter
Drawing Not To Scale
Liquid Hydrogen-Based Refueling Station Site Plan
High Pressure Cascade
Storage System
H2 Dispensing Island
NFPA 50A Minimum Set-backs for
gaseous hydrogen storage
Walls with minimum fire rating of2 hr 5ft
Wall openings (doors & windows) 25 ft
Intake vents 50 ft
Adjoining property line thatcanbe builton 5ft
Places ofpublic assembly 50 ft
Public sidewalks and parked vehicles 15 ft
Gasoline Storage 50 ft
Heat
Exchanger/
Vaporizer
Compressor
Convenient Store &
Fuel Retail Center
Liquid Hydrogen
Truck Delivery Area
NFPA 50B Minimum Set-backs for
liquid hydrogen storage (1994)
Intake vents 75 ft
Adjoining property line thatcanbe builton 25 ft
Public sidewalks and parked vehicles 25 ft
TIAX LLC
8/5/03
Liquid Hydrogen
Storage
5000 gal
Figure 4-5. Liquid Hydrogen-Based Refueling Station Site Plan
4-9
4.2 Electrolyzer Documentation
Process Description
Electrolysis is the process of splitting water into hydrogen and oxygen with electricity by
transmitting an electrical current through an electrolyte. Oxygen and hydrogen gases
are produced at the anode and the cathode respectively, separated from the electrolyte
and gathered in separate vessels for further processing. The anode is the electrode
through which the electrons leave the electrolytic cell and produces gaseous oxygen.
The reaction at the anode is:
+ + e O H O OH 2
2
1
2
2 2
Similarly, the cathode is the electrode where electrons enter the electrolytic cell and
promote the combination of hydrogen ions per the following reaction:

+ + OH 2 H e 2 O H 2
2 2
Alkaline and Solid Polymer Electrolyte Membranes (SPEM) are the two most common
types of electrolysis used for hydrogen production. For this study, the electrolyzer-based
hydrogen refueling station is an alkaline electrolyzer. Alkaline is the oldest electrolysis
technology and the one most typically used for large-scale electrolytic hydrogen
production. Many of todays units operate near ambient pressures and at temperatures
between 80 and 145 C. The system in this study operates at 150 psi; the higher output
pressure reduces compression costs.
Equipment Description
The key components of an electrolyzer system include:
Cells and electrodes: Alkaline electrolyzers require the use of gas separators between
the electrodes to prevent the migration of hydrogen to the oxygen side and vice versa.
The electrodes must be able to withstand highly corrosive environments, be highly
conductive, and have high surface activity. Hence, the electrodes are commonly porous
and are usually constructed of nickel-based catalysts.
Water Purification: Demineralizer and carbon filter cartridges produce high quality water
required by the process.
Gas Generation System and Seals/KOH Handling: Conductivity sensor, leak detector,
feed water bowl level sensor, feed pumps, cell stack temperature and water level
control, ventilation blower, water seals, demisters, hydrogen ballast and hydrogen gas
analyzer, a deoxydizer and peripheral cell components.
4-10
Hydrogen Purification and dryer system: A twin bed regenerative molecular sieve dryer,
coalescing filters, and carbon adsorption filters provide clean contaminant free hydrogen
for storage,
Table 4-3 summarizes typical equipment and utility specifications. Table 4-4 is a
summary of the codes and standards applicable to electrolyzer-based system. Figures
4-6 through 4-8 show the representative PFD, P&ID, and site plans. Table 4-5 presents
a typical station operating procedures, and Table 4-6 presents the various safety
measures.
Table 4-3. Electrolyzer Equipment and Product Specification
Item Specification
System Power Supply 480 V, 3-Phase, 60 HZ
Power 325 kVA
Electrolyzer Cells 10 cell stack
Design Current 620 A DC
Cell Voltage 1.9V
Operating Temperature 63
o
C Max.
Operating Pressure 150 psig
Electrolyte 34% KOH
Feedwater Flowrate Total 4 GPH
Feedwater Supply Demineralized
Flow rate 4 GPH
Hydrogen Catalytic Purifier Rated 02 PPM by Vol: 2-5
Operating Pressure 250 psig max.
o
C max.
Hydrogen Dryer Operating Pressure 250 psig max.
o
C
Rated Dew point 55
o
C
Product Hydrogen 99.99% purity hydrogen
1.25 kg/h, 8.6 scfm
Piping Systems In conformance with :
ASME B31.8: Gas Transmission & Distribution Piping
Systems for process piping
CGA G-5.4: Standard for Hydrogen Piping Systems at
Consumer Location hydrogen piping
Equipment and Area Classification Electrical equipment in conformance with NFPA 70
Unclassified ventilated enclosure
Other Equipment
1.25 kg/h, 8.6 scfm
Compressed Hydrogen Storage
Vessels
78 kg H
2
capacity
3.03 WC m
3
H2 capacity at 6,250 psi
Compressed Hydrogen Dispenser Fueling at 5,000 and 3,600 psi
4
-
1
1
STORAGE
DISPENSER
T P
H
2
O H
2
O
2
1 Electricity, 325 kVA
2 Feed Water (34% KOH) 15.00 20 5
3 Electrolysis Gas 1.25 0.63 80 10
4 Purified Product Hydrogen 1.25 40 10
5 High Pressure Compressed Hydrogen 1.25 40 425
6 Compressed Hydrogen Storage @ 6,250 psig (78 kg cap.) 20 425
7 Compressed Hydrogen to Dispenser from Storage 30 20 340
8 Exhaust Oxygen 0.63 40 1
Atm
Stream # Description
o
C
Composition
kg/h
H
2
O
(34% KOH)
ELECTRICITY
1
2
3 4
5
6
7
8
ELECTROLYZER
Figure 4-6. Electrolyzer-Based Refueling Station Process Flow Diagram
4
-
1
2
H2O
(34%KOH)
ELECTRICITY
ELECTROLYZER
OXYGENTO
VENT
STORAGE
HYDROGENTO
DISPENSER
HYDROGENTO
VENT
RECTIFIER
DEMINERALIZER
KOH
STAGES 1 & 2
CATALYTIC
PURIFIER
TO BALLAST
DRYER
STAGES 3 & 4
Level Indicator
CI
Conductivity Indicator
Oxygen Indicator
LI
CI
TI
O
2
I
PI
PI
LI
TI
LI
TI
O
2
I
P
I
TI
TI
HYDROGENTO
VENT
2
I
H
2
I
LI
TI
O
2
SEAL/
DEMISTER
BALLAST
Propertyof:
TIAX LLC
1061 De Anza Blvd.
Cupertino, CA 95014
Hydrogen Fueling Station - Onsite Electrolyzer
SI ZE DWGBY DWGNO REV
B J ohnWoody D130-P-2001 1a
SCALE Not to Scale 07/16/03 SHEET 1 OF 1
PI
DP
H
2
SEAL/
DEMISTER
A
A
A
A
A
Figure 4-7. Piping and Instrumentation Diagram for Electrolyzer-Based Refueling
4-13
Table 4-4. Codes and Standards Regarding Compressed Hydrogen Storage
Distance from Gaseous Hydrogen Storage
Element of Station NFPA 50A IFGC 704.2 IFC 2209.3.1.1
Walls with Minimum Fire Rating 5 ft (2-hour)
Wall Openings (doors & windows) 25 ft
Intake Vents 50 ft
Lot Line 5 ft 10 ft 15 ft
Places of Public Assembly 50 ft
Parked Vehicles 15 ft
Overhead Electric Wire 5 ft 0 ft
Cement Block Wall 0 ft 0 ft 5 ft
Public Sidewalks 15 ft 10 ft 15 ft
Office/Store
Building having noncombustible wall
surfaces that are not part of a 1 hour fire
resistant-rated assembly
25 ft
0 ft w/2-hour wall
10 ft 25 ft
Gasoline and Hydrogen Dispensing 10 ft 15 ft
HVAC, Doors, and Windows 15 ft
4
-
1
4
Bollard
Security Fence
Gasoline/Diesel
Dispensing Islands
Electrolyzer-Based Refueling Station Site Plan
Convenient Store &
Fuel Retail Center
Electrolyzer Cel l s
KOH System
Puri fier/Dr yer
Hi gh-Pr essur e
Compressor
Storage System
Walls withminimum fireratingof2 hr 5 ft
Intakevents 50 ft
Adjoining property line thatcan be builton 5 ft
Public sidewalks andparkedvehicles 15 ft
Underground
Gasoline Storage
TIAX LLC
8/1/03
Figure 4-8. Electrolyzer-Based Refueling Station Site Plan
4-15
Table 4-5. Electrolyzer-Based Refueling Station Operating Procedures
Step
Key Equipment
Involved Example Operating Sequences
1 System Startup
& Operation
Electrolyzer
KOH System
Auxiliary Cooling
System
Purification/Drying
Compression
Storage System
Initiate following start-up sequence using a
computerized SCADA system Turn ON switch to
result in the following actions
1. Start cooling water circulation and air cooling
blower fans
2. Fill cells with electrolyte solution (34% KOH) to
operating levels.
3. Power Rectifier. Start current ramp-up
4. Enable normal feed of all electrolyte cells
5. Start 3-stage high-pressure compressor system to
storage system when hydrogen flow-rate and line
pressure set-points are reached
6. Shut down power to rectifier when storage system
set-point pressure of 6,250 psig is reached.
2. System
Shutdown
Electrolyzer
KOH System
Auxiliary Cooling
System
Purification/Drying
Compression
Storage System
computerized SCADA system Turn OFF switch to
result in the following actions.
1. Shut down power to rectifier
2. Shut down compressor system
3. Turn-on purge/blanket Nitrogen valve
4. Allow system to reach off set-point temperature
of ambient
5. Shut down cooling water and air blowers
3. Dispensing/
Vehicle
Refueling
Dispenser
Vehicle
Dispensing follows the CA FCP protocol for vehicle
fueling including communication with the vehicle
and dispenser
Dispenser is activated with a card-lock/PIN
mechanism
Following connection of the hose with the correct
receptacle (5,000-psi vs. 3,600-psi) fueling
commences
When fueling is complete, dispenser is turned off.
The receptacle release lever also serves to vent
fugitive gas back to the dispenser.
4-16
Table 4-6. Electrolyzer-Based Refueling Station Safety Measures
Safety Example Measures
Equipment The e le c tr oly ze r un it op e ra te s u nd er a pr es s ur e o f 12 5 p sig a nd is d es ig n ed for
2 75 p sig . Th e r ec tifie r h as o utp ut a mpe ra ge of 6 2 0 AD C a nd is e qu ip p ed w ith
a utomatic sh u t- off s witc h es for te mp e ra tu re an d p ow er o v er lo a d co nd ition s . Th e
e le ctro lyz er un it r o om is d es ig n ed w ith a minimu m 5 -ft s afety a nd ma in te n an ce
e nv elop e a nd in c omp lian c e with NFPA 70 s ta n da rd s .
The compressor system is equipped with safety relief valves. Safety switches
connected to the overall system PLC, and OSHA standard belt guards.
The storage tanks store compressed hydrogen gas at 6,250 psi. These tubes
are also designed to ASME standards with a design pressure of 7,255 psi,
and tested to 1.5 times that level. The tanks are equipped with relief valves to
release any overpressure.
The two dispensers operate at pressures of 5,000 psi and 3,600 psi
respectively. They utilize connectors that include over-pressure protection,
remote shutoff capability, a breakaway connector (in case the car is driven
away while the fill hose is attached) and non-interchangeable nozzles (to
prevent inadvertent use of a 5,000 psi dispenser with a car designed with a
3,600 psi tank).
Process Maintenance activities follow OSHA 1910.147 lock-out tag-out procedures.
The entire refueling system is designed for unattended operation for extended
periods and can be monitored locally via a PC. The system is designed for fail
safe shutdown and is provided with an emergency stop button and a remote
shutdown contact. The unit can also be shutdown via the PLC. The system
includes redundant combustibles detectors, a CO monitor and a fire detection
system.
Dispensing follows the CAFCP protocol for vehicle fueling including
communication with the vehicle and dispenser.
Site If not placed in a ventilated enclosure, equipment located in the hydrogen
generator room is rated for Class I, Div. 2, Group B service.
The control system is located outside of the hydrogen generator room in a
non-hazardous area classification.
4-17
4.3 Steam Methane Reformer (SMR) Documentation
4.3.1 Hydrogen Generation
Process Description
Devices that produce hydrogen by reacting hydrocarbons with water are called
reformers. The initial reaction products are principally hydrogen plus carbon monoxide,
which is sometimes combined with more water in a shift reactor to produce hydrogen
plus carbon dioxide. Natural gas is the most commonly used feedstock, although
reformers can be designed to process almost any hydrocarbon. Steam methane
reformers use methane, the principal constituent of natural gas, and steam to generate
hydrogen. The overall reaction can be written as:
CH
4
+ H
2
O CO + 3H
2
A typical SMR hydrogen generator consists of two main elements - the fuel processor
and the pressure swing adsorption (PSA) purification unit. The fuel processor generates
a reformate containing about 75 percent hydrogen. The fuel processor consists of a
natural gas compressor, a desulfurizer to remove impurities from the natural gas
feedstock, a preheat section, a steam-reformer, a high temperature shift reactor, a
waste heat recovery steam generator, a process gas cooler, and a condensate
separator. The fuel processor operates at about 120 psig pressure to produce reformate
that can be sent directly to the PSA without further compression. The desulfurizer will
remove impurities such as odorants and hydrogen sulfide. The steam reformer will
convert the natural gas feedstock by reaction with steam to a synthesis gas containing
relatively high concentrations of CO (8-10 dry vol. percent).
The shift reactor will reduce the CO concentration to less than 4.0 dry vol. percent. The
process gas cooler and condensate separator will condense and recover moisture from
the steam reforming process. The waste heat recovery steam generator will recover
waste heat from the reformer flue gas and the process gas to generate steam for
reforming. Hydrogen is purified in the PSA to a product containing >99.99 percent
hydrogen and less than five ppm CO. Lower CO concentrations can be achieved but at
slightly reduced recovery efficiency. PSA tail gas consisting primarily of CO and other
residual hydrocarbons is used as the reformer burner fuel.
Equipment Specifications
The on-site small-scale SMR plant uses the on-site natural gas for feed and as start-up
fuel, de-ionized water for steam generation, and 208-240 VAC/60 Hz/ 3-phase
electricity. Nitrogen is used to purge the system. The SMR is designed to produce
4-18
1.25 kg/h hydrogen. The system has a connection to a flue gas vent, a process safety
valve relief vent, liquid drain line and a product hydrogen effluent line.
The unit is capable of unattended operation for extended periods and can be monitored
locally via a personal computer. The SMR plant is designed for fail safe shutdown and is
provided with an emergency stop button and a remote shutdown contact. The unit can
also be shutdown via the PLC. The unit includes a combustibles detector, a CO monitor,
and a fire detection system. All equipment located in the SMR cabinet/room is rated for
Class I, Div. 2, Group B service. The control system is located outside of the hydrogen
generator room in a non-hazardous area classification.
Table 4-7 summarizes typical equipment and utility specifications. Table 4-8 is a
summary of the codes and standards applicable to SMR-based system. Figures 4-9
through 4-11 show the representative PFD, P&ID, and site plans. Table 4-9 presents a
typical station operating procedures, and Table 4-10 presents the various safety
measures.
4-19
Table 4-7. SMR/PSA Equipment and Product Specification Summary
Item Specification
Generator Rated Capacity 1.25 kg/h
Delivery Pressure 150 psig
Delivery Temperature 40C
Natural Gas Feed rate @ 6 w.c. 5.04 kg/h
Deionized Water Feed rate 2.5 GPM demineralized
Power Requirements 208-240 VAC/60Hz 3-Phase
Generator Turndown Ratio 3:1
Equipment and Area
Classification
Electrical equipment in conformance with NFPA 70
Class I, Division 2, Group B Service
Ventilated enclosure
Product Hydrogen Specification 99.99% purity Hydrogen
<5 ppm CO
Other Equipment
1.25 kg/h flow rate
Compressed Hydrogen Storage
Vessels
78 kg H
2
capacity
2.88 WC m
3
H
2
capacity
Compressed Hydrogen
Dispenser
Fueling at 5,000 and 3,600 psi
4
-
2
0
1
2
3
4
5
6
7
8
9
10
STEAM METHANE
REFORMER
PURIFIER
PSA
STORAGE
DISPENSER
AIR
H
2
O
NATURAL
GAS
T P
N a t. G a s A i r O 2 N 2 H 2 O H 2 C O 2 C O T H C N O x
o
C
A tm
1 F e e d N a t u ra l G a s 5 . 0 4 4 0 2
2 F e e d W a t e r 1 3 . 3 8 2 0 1 0
3 R e f o rma t e H yd ro g e n 5 . 9 2 1 . 6 7 5 . 4 6 4 . 8 7 0 . 3 6 4 0 1 0
4
Pu rif ie d Pro d u ct H yd ro g e n f ro m
PSA t o C o mp re sso r 1 . 2 5 4 0 1 0
5
H ig h Pre ssu re C o mp re sse d
H yd ro g e n t o St o ra g e 1 . 2 5 4 0 4 2 5
6 C o mp re sse d H yd ro g e n St o ra g e 2 0 4 2 5
7
C o mp re sse d H yd ro g e n t o
D isp e n se r f ro m St o ra g e 1 8 . 0 0 2 0 3 4 0
8 PSA R e sid u a l t o R e f o rme r a s F u e l 0 . 1 4 0 . 1 2 0 . 4 2 5 . 4 6 4 . 8 7 0 . 3 6 4 0 1
9 R e f o rme r C o mb u st io n Air 3 2 . 4 5 7 . 5 6 2 4 . 8 9 2 5 1
1 0 R e f o rme r C o mb u st o r Exh a u st Ga s 2 5 . 0 3 1 . 9 2 1 4 . 1 1 2 . 0 E-0 4 6 4 1
C o m p o s i ti o n (k g / h )
Stre a m # D e s c ri p ti o n
Figure 4-9. SMR-Based Station Process Flow Diagram
4
-
2
1
STEAMMETHANE
REFORMER
PURIFIER
PSA
AIR
H2O
NATURAL
GAS
3600 PSI
6250 PSI
Propertyof:
TIAX LLC
1061DeAnzaBlvd.
Cupertino,CA 95014
Hydrogen Fueling Station - Onsite SMR with PSA
SIZE DWGBY DWGNO REV
B J ohnWoody D130-P-3001 1a
SCALE Not toScal e 07/25/03 SHEET 1OF 1
B
A
4 3 2 1
B
A
4 3 2 1
HYDROGEN TO
VENT
Level Indicator
Conducti vity Indicator
OxygenIndi cator
LI
CI
TI
O
2
I
2
I
Oil Pressure Indicator OPI
SA Seal Failure Alarm
RuptureDisk
Hydrostatic Relief Valve
PDIT
PDIT
HYDROGENTO
DISPENSER
TI
LI
DEMINERALIZER
CI
A A
A
A
A
A
A
A
TI
TI
TI
TI
CW
Figure 4-10. Piping and Instrumentation Diagram for Steam Methane Reforming-Based Refueling
4-22
Walls with Minimum Fire Rating 5 ft (2-hour)
Wall Openings (doors & windows) 25 ft
Intake Vents 50 ft
Places of Public Assembly 50 ft
Parked Vehicles 15 ft
Public Sidewalks 15 ft 10 ft 15 ft
Office/Store
surfaces that are not part of a 1 hour fire
resistant-rated assembly
25 ft
0 ft w/ 2-hour
wall
10 ft 25 ft
HVAC, Doors, and Windows 15 ft
4
-
2
3
Bollard
Security Fence
Gasoline/Diesel
Dispensing Islands
Electrolyzer-Based Refueling Station Site Plan
Convenient Store &
Fuel Retail Center
Electrolyzer Cel l s
KOH System
Puri fier/Dr yer
Hi gh-Pr essur e
Compressor
Storage System
Walls withminimum fireratingof2 hr 5 ft
Intakevents 50 ft
Adjoining property line thatcan be builton 5 ft
Public sidewalks andparkedvehicles 15 ft
Underground
Gasoline Storage
TIAX LLC
8/1/03
Figure 4-11. SMR-Based Refueling Station Site Plan
SMR
Compressor
PSA Purifier
4-24
Table 4-9. SMR-Based Refueling Station Operating Procedures
Step Key Equipment Involved Example Operating Sequences
1 System Startup &
Operation
Reformer
Air Blower
Water Pump
NG Compressor
PSA System
Compression System
Storage System
computerized SCADA system Turn ON switch
to result in the following actions
1. Start Air Blower
2. Open NG and water valves from city mains
3. Open secondary NG valve to reformer burner
4. Reformer burner ignition
5. Reformer combustion chamber reaches set-
point temperature of 1,400
o
F
6. Open primary water feed valve to reformer
7. Open NG feed valve to reformer
8. Start PSA system
9. Open PSA residue valve to primary reformer
burner
10. Close secondary NG supply valve to reformer
burner
11. Start 3-stage high-pressure compressor
system to storage system when PSA output
H2 concentration reaches 99.8%
12. Storage system set-point pressure @ 6,250
psig
13. Reformer turn-down and hydrogen reburn on
when storage system has attained set-point
pressure
2. System Shutdown Reformer
Air Blower
Water Pump
NG Compressor
PSA System
Compression System
Storage System
computerized SCADA system Turn OFF switch
to result in the following actions.
Shut down feed NG and water valves
Turn-on purge/blanket Nitrogen valve
Shut down PSA and Compression systems
Reformer combustion chamber reaches off
set-point temperature of ambient
Shut down air blower
3. Dispensing/Vehicle
Refueling
Dispenser
Vehicle
Dispensing follows the CA Fuel Cell
Partnership protocol for vehicle fueling
including communication with the vehicle and
dispenser
mechanism
Following connection of the hose with the
correct receptacle (5,000-psi vs. 3,600-psi)
fueling commences
When fueling is complete, dispenser is turned
off. The receptacle release lever also serves to
vent fugitive gas back to the dispenser.
4-25
Table 4-10. SMR-Based Refueling Station Safety Measures
Equipment The reformer reactor vessel and combustion chamber are designed to
ASME standards with a design pressure of 250 psig. The reactor operates
at a pressure of 125 psig. The reactor is equipped with relief valves to
release any over pressure.
The compressor system is equipped with safety relief valves. Safety
switches connected to the overall system PLC, and OSHA standard belt
guards.
The storage tanks store compressed hydrogen gas at 6,250 psi. These
tubes are also designed to ASME standards with a design pressure of
7,255 psi, and tested to 1.5 times that level. The tanks are equipped with
relief valves to release any overpressure.
3,600 psi tank).
Process The entire refueling system is designed for unattended operation for
extended periods and can be monitored locally via a PC. The system is
designed for fail safe shutdown and is provided with an emergency stop
button and a remote shutdown contact. The unit can also be shutdown via
the PLC. The system includes redundant combustibles detectors, a CO
monitor and a fire detection system.
Dispensing follows the CA Fuel Cell Partnership (CaFCP) protocol for
vehicle fueling including communication with the vehicle and dispenser.
Site In the absence of a forced ventilation enclosure, all equipment located in the
hydrogen generator room is rated for Class I, Div. 2, Group B service.
4-26
4.4 Tube Trailer Documentation
Process Description
The compressed hydrogen refueling station is comprised of a tube-trailer system.
Relatively speaking, the tube-trailer is a simple and low-capital expense way to provide
hydrogen fueling for vehicles. Hydrogen gas is stored in the tube trailer, roughly at an
operating pressure of 3,200 psig, which feeds the compressor system. After
compression, the gas is stored in buffer storage tanks and then dispensed on board the
vehicles. The trailer assembly is not a permanent fixture and is refilled off-site.
Connections to the trailer utilize a permanent tubing system. A tube trailer consists of a
pack of pressurized cylinders connected by a manifold and housed on a trailer.
4.4.1 Equipment Description
The tube trailer holds about 343 kg (137,500 scf) of hydrogen at an operating pressure
of 3,200 psi. Typical dimensions for the trailer are 40 to 45 feet long, 10 feet high and 8
to 9 feet wide. The hydrogen storage tubes are Type IV DOT and NHTSA certified, with
a burst-disc/fusible-metal pressure-relief-device (PRD) providing over pressure
protection. This device is screwed directly into the bottle with a vent line that directs
vented gas to a safe location.
Table 4-11 summarizes the typical equipment and utility specifications. Table 4-12 is a
summary of the codes and standards applicable to compressed hydrogen/tube trailer
system. Figures 4-12 through 4-14 show the representative PFD, P&ID, and site plans.
Table 4-13 presents a typical station operating procedures and Table 4-14 presents the
various safety measures.
4-27
Table 4-11. Tube Trailer and Compressed Hydrogen Equipment and Product
Specification
Item Specification
Tube Specifications 38-ft long
14-inch OD
0.409-inches minimum wall thickness
34.2 cu-ft water volume/each
2,500 lb/each
3,129 psi maximum allowable pressure
103,102 scf hydrogen payload @ max. pressure
Tube Certification DOT 3T
Type IV
Equipment and Area
Classification
Electrical equipment in conformance with NFPA 70
Class I, Division 2, Group B Service
Explosion proof equipment in open area
Other Equipment
Tube Trailer Delivery Truck
14-ft clearance, 40-ft trailer
Class 8 Tractor
Hydrogen Compressor Compression to 6,250 psi
4 kg/h nominal
Compressed Hydrogen
Storage Vessels
30 kg H
2
capacity
1.21 WC m
3
H
2
capacity
Compressed Hydrogen
Dispenser
Fueling at 5,000 and 3,600 psi
4
-
2
8
STORAGE
DISPENSER
Composition T P
H
2
kg/h
1 Delivered Hydrogen 3.70 20 215
2 High Pressure Compressed Hydrogen 3.70 40 425
3 High Pressure Gas Storage 20 425
4 Compressed Gas to Dispenser from Storage 30 20 340
Stream # Description
o
C
Atm
2
3
4
1
Figure 4-12. Tube Trailer Delivery-Based Refueling Station Process Flow Diagram
4
-
2
9
STORAGE
Property of:
TIAX LLC
1061 De Anza Blvd.
Cupertino, CA 95014
Hydrogen Fueling Station - Tube Trailer Delivery,
Compressed Hydrogen
SIZE DWG BY DWG NO REV
B J ohn Woody D130-P-4001 1a
SCALE Not to Scale 07/24/03 SHEET 1 OF 1
PI
Temperature Indicator TI
Pressure Indicator
PI
Hydrogen Indi cator H
2
I
Oil Pressure Indi cator
OPI
SA Seal Fai l ure Al arm
Pressure Reli ef Val ve
Rupture Disk
Hydrostati c Reli ef Val ve
OPI
SA
HYDROGEN TO
DISPENSER
HYDROGEN TO
VENT
A
A
A
Figure 4-13. Piping and Instrumentation Diagram for Tube Trailer Delivery-Based Refueling
4-30
Walls with minimum fire rating 5 ft (2-hour)
Intake vents 50 ft
Places of public assembly 50 ft
Parked vehicles 15 ft
Public sidewalks 15 ft 10 ft 15 ft
Office/Store
surfaces that are not part of a 1 hour
fire resistant-rated assembly
25 ft
0 ft w/ 2-hour wall
10 ft 25 ft
HVAC, doors, and windows 15 ft
4
-
3
1
Security Fence
Compressed Hydrogen Delivery -Based Refueling Station Site Plan
Storage System
Wall openings (doors & windows) 25ft
Intake vents 50ft
Adjoining property line thatcan be builton 5ft
Places ofpublic assembly 50ft
Public sidewalks andparkedvehicles 15ft
Gasoline Storage 50ft
Compressor
Convenient Store &
Fuel Retail Center
Tube Trai ler Truck
Del ivery Area
TIAX LLC
8/14/03
Figure 4-14. Compressed Hydrogen Delivery-Based Refueling Station Site Plan
4-32
Table 4-13. Tube Trailer Delivery-Based Refueling Station Operating Procedures
Step
Key Equipment
Involved Example Operating Sequences
1 System Startup &
Operation
Tube-Trailer
High Pressure
Hydrogen Storage
Compressor
computerized SCADA system Turn ON switch to
result in the following actions
1. Turn system power on.
2. When high-pressure storage bank pressure falls
below set-point pressure (~6,200 psi), open tube-
trailer storage system main outlet valve.
3. Start compressor and fill up high-pressure storage
bank to set-point pressure.
4. Stop compressor after set-point pressure is
reached.
5. Close main outlet valve of step 1.
2. System Shutdown Tube-Trailer
High Pressure
Hydrogen Storage
Compressor
computerized SCADA system. Turn OFF switch to
result in the following actions:
6. All distribution valves to normally-close position.
7. Turn system power off.
3. Dispensing/Vehicle
Refueling
Dispenser
Vehicle
Dispensing follows the CA FCP protocol for vehicle
fueling including communication with the vehicle and
dispenser.
mechanism
Following connection of the hose with the correct
receptacle (5,000-psi vs. 3,600-psi) fueling
commences.
When fueling is complete, dispenser is turned off.
The receptacle release lever also serves to vent
fugitive gas back to the dispenser.
4-33
Table 4-14. Tube Trailer Delivery-Based Refueling Station Safety Measures
Equipment The tube-trailer is designed to DOT 3T Type IV and NHTSA standards. The
tubes on the trailer are secured on an ASME receiver assembly.
The high-pressure compressor system is equipped with safety relief valves,
safety switches connected to the overall system PLC, and OSHA standard
belt guards.
The storage tanks store compressed hydrogen gas at 6,250 psi. These
tubes are also designed to ASME standards with a design pressure of
7,255 psi, and tested to 1.5 times that level. The tanks are equipped with
relief valves to release any overpressure.
3,600 psi tank).
Process Maintenance activities follow OSHA 1910.147 lock-out tag-out procedures.
The entire refueling system is designed for unattended operation for
extended periods and can be monitored locally via a PC. The system is
designed for fail safe shutdown and is provided with an emergency stop
button and a remote shutdown contact. The unit can also be shutdown via
the PLC. The system includes redundant combustibles detectors, a CO
monitor and a fire detection system.
Dispensing follows the CAFCP protocol for vehicle fueling including
communication with the vehicle and dispenser.
Site In the absence of a forced ventilation enclosure, all equipment located in
the hydrogen generator room is rated for Class I, Div. 2, Group B service.
4-34
4.5 Compressed Natural Gas (CNG) Documentation
4.5.1 Natural Gas Refueling Station Major Components
Production/Delivery
Pipeline natural gas is delivered at three to 40 psig. The available gas pressure varies
with each site. Higher supply pressures will enable using a compressor with one less
stage and lower power requirements. Natural gas supply pressures as high as 200 psi
may be available at some industrial sites. Prior to compression, a dryer removes
moisture and heavy hydrocarbons.
4.5.2 Refueling Station Nominal Design Basis
Table 4-15. CNG Fueling Station Common Design Bases
Number of vehicles refueled 10 per day
Number of vehicles per hour 5 per 2-hours
Vehicle refueling capacity 7.4 therms-CNG/fill (743 scf/fill)
Vehicle refueling time 10 min/vehicle
Station maximum average consumption 7430 scf-CNG/day
The assumed energy consumption (in Btu/mile) of the CNG vehicles is roughly twice
that of an identical hydrogen fuel cell vehicle. The relationship between CNG and
hydrogen vehicle energy consumption would be different for dissimilar vehicle or power
plant configurations.
CNG Compression
The power required for CNG compression depends on the compressor inlet and exit
pressure, compressor configuration, and motor. A 4-stage reciprocating compressor,
intercooled, lubricated, 4,500-psi discharge pressure, 600 scfh, 200-hp electric motor
driven compressor is specified for use at this site. The compressor is located outside.
Enclosure mounted compressor systems are also used in the CNG industry but were
not assumed for this configuration. The configuration of the CNG system is similar to the
hydrogen tube trailer discussed in Section 4.4.
4-35
High Pressure CNG Storage
Process Description
All CNG fueling stations include some form of high-pressure gas storage prior to the
dispenser. This storage is either a buffer or cascaded pressure vessel(s), and its
capacity can range from small to large.
A bank of two high-pressure storage vessels with a total capacity of 200 therms of CNG
is specified.
High Pressure CNG Dispensing System
Process Description
The dispenser draws from the high-pressure gas storage system described in the
previous section. The controller for the cascade, which is called a priority-sequencing
controller, is part of the dispenser. The priority sequencing controller has fully
programmable set points for directing the gas supply from the different banks (i.e., at a
common pressure) of storage vessels to the dispenser. The set points for switching the
gas supply from different banks of storage vessels are selected to suit fueling
requirements such as the quantity of CNG to be dispensed. A heat-of-compression
algorithm is used by the dispenser to predict the quantity of gas to be dispensed into the
fuel tank that will provide a full fill, or the fullest possible fill, within tank pressure and
temperature constraints. The fueling nozzles have a lever that actuates a three-way
valve that allows gas (that would otherwise be trapped at the end of the fill) to be vented
back to the dispenser through a vent hose.
For this specific site, the dispenser is equipped with 3,600 psi nozzles. Fill hoses are
reinforced and rated for high-pressure CNG service. The hose is connected to the
dispenser by a break-away device. This coupling is designed to prevent natural gas
release in case a vehicle drives away from the dispenser with the nozzle still connected
to the receptacle. The break-away device disconnects when subjected to relatively low
tensile loads or bending moments. Poppet valves in each segment spring close to stop
the natural gas flow. Access to a CNG dispenser is controlled by a card lock system
with PIN access.
4-36
Table 4-16 summarizes the typical equipment and utility specifications. Table 4-17 is a
summary of the codes and standards applicable to CNG station. Figures 4-15 through
4-17 show the representative PFD, P&ID, and site plans.
Table 4-16. Compressed Natural Gas Equipment and Product Specification
Item Specification
System Power Supply 480 V, 3-Phase, 60 HZ
Power 325 kVA
Natural Gas Feed Line Delivery at 3-40 psi
Natural Gas Compressor Compression to 4,500 psi
2.5 kg/h flowrate
Explosion proof equipment in open area
Compressed Natural Gas Storage Vessels 20,000 scf of natural gas capacity
4,500 psig
144 kg CH
4
capacity
14.4 WC m
3
CH
4
capacity
Compressed Natural Gas Dispenser Fueling at 3,000 and 3,600 psi
4
-
3
7
STORAGE
DISPENSER
Composition T P
Natural Gas
kg/h
1 Feed Natural Gas 18.0 20 2
2 High Pressure Compressed Natural Gas 18.0 40 310
3 High Pressure Gas Storage 20 310
4 Compressed Gas to Dispenser fromStorage 150 20 310
Atm Stream # Description
o
C
2
3
4
NATURAL
GAS
1
Figure 4-15. Compressed Natural Gas Refueling Station Process Flow Diagram
4
-
3
8
NATURAL GAS TO
DISPENSER
NATURAL GAS TO
VENT
STORAGE
NATURAL
GAS
Property of:
TIAX LLC
1061 De Anza Blvd.
Cupertino, CA 95014
Compresed Natural Gas Station - CNG Delivery via
Pipeline
SIZE DWG BY DWG NO REV
B J ohn Woody D130-P-5001 1a
SCALE
Not to Scale 07/24/03
SHEET
1 OF 1
Oi l Pressure Indi cator OPI
Pressure Reli ef Val ve
OPI
B
B
B
Figure 4-16. Piping and Instrumentation Diagram for Compressed Natural Gas Refueling
4-39
Table 4-17. Codes and Standards Regarding
Compressed Natural Gas Storage
Distance from Gaseous
Natural Gas Storage
Element of Station NFPA 52
Point of Transfer 3 ft
Lot Line 10 ft
Public sidewalks or streets 10 ft
Railroad Track 50 ft
Readily Ignitable Material 10 ft
Ignition Source 10 ft
4
-
4
0
Security Fence
Compressed Natural Gas Refueling Station Site Plan
Storage System
Natural Gas
Dispensing Island
NFPA 52 Minimum Set-backs for
gaseous natural gas storage
Railroadtrack 50ft
Pointoftransfer 3 ft
Adjoining property line thatcan be builton 10ft
Readily ignitable material 10ft
Public sidewalks or streets 10ft
Abovegroundtanks containing
flammable or combustible liquids
20ft
Compressor
Mai ntenance Buil ding
TIAX LLC
8/14/03
Natural Gas
Pipeline
Figure 4-17. Compressed Natural Gas Refueling Station Site Plan
5-1
5. COMPARISON OF HYDROGEN AND OTHER
FUELS
5.1 Introduction
The question of whether hydrogen is safer or more dangerous than gasoline, diesel, or
other fuels does not have a simple answer for the following reasons:
The relative safety of different fuels is highly scenario dependent. Fuel leaks from a
high-pressure fitting in a closed garage with an overhead garage-door opener are
more likely to be an issue for hydrogen than for gasoline. Carbon monoxide
poisoning can be an issue for gasoline and other fuels but not for hydrogen. We can
apply scientific methods such as failure modes and effects analysis (FMEA) to
predict the frequency and consequences associated with using different fuels in
different scenarios. The difficult part is quantifying the relative frequency of
completely different scenarios.
Because hydrogen use as an automotive fuel is in its infancy, we simply cannot
compare hydrogen and gasoline vehicle accident statistics. Even when hydrogen
vehicle accident data do become available, work with gasoline vehicle accident data
shows that it is often not straightforward to segregate accidents where the fuel did or
did not play a role in the accident cause or effect (e.g., accident reports from many
states do not note if the vehicle caught fire). While there are historical data
pertaining to hydrogen use in industrial, aerospace, and other applications, the
application of these data to hydrogen-fueled vehicles is questionable.
The newness of hydrogen fuel use renders judgment problematic when considering
the specific vehicle and fueling station design features affecting potential accidents.
What types of safety features will hydrogen vehicles and fueling stations have?
Various groups are working to develop codes and standards that will eventually
answer this question.
While it is not possible to rank the absolute overall safety of hydrogen-fueled vehicles at
this time, it is possible to compare the general safety issues associated with hydrogen
and other fuels. General safety concerns derive primarily from the different physical and
chemical properties of different fuels and from the scenarios for which these properties
might make an accident more likely. The following sections compare the properties of
hydrogen with other fuels. This provides the basis for the discussion of the different
safety issues associated with these fuels.
5-2
5.2 Hydrogen Properties
Table 5-1 lists some of the key chemical and physical properties of hydrogen and six
other fuels: natural gas, liquefied petroleum gas (LPG), methanol, ethanol, gasoline,
and diesel fuel. Table 5-1 presents data abstracted from many sources (DOE AFDC,
Kirk, NASA 1997, Murphy, Browning, AGA 1981, Perry, and Peschka). This fuel
property comparison provides a basis for discussing the different safety issues
associated with different fuels and the circumstances in which hydrogen is likely to be
safer or less safe than other fuels.
The data in Table 5-1 should be interpreted and used with caution. The notes to Table
5-1 list some important caveats. A factor that makes such fuel property comparisons
ambiguous is that some of the fuels are imprecisely defined. While hydrogen is
generally regarded as nearly pure hydrogen, particularly if it is used for fuel cell
vehicles, the definitions of the other fuels are not as simple. Gasoline and diesel fuel are
designations applied to fuels that can have a range of compositions depending on
geographic location, season, applicable regulations, grade (e.g., octane rating), and
manufacturer. Natural gas and LPG compositions also vary significantly, and the
composition of CNG is usually different from LNG, which contains essentially no carbon
dioxide, water vapor, or sulfur compounds. Table 5-1 lists gasoline and diesel fuel
properties for typical compositions, and some fuel blends can have properties that
depart significantly from these values. Natural gas and LPG are assumed to consist of
100 percent methane and propane, respectively, in order to avoid the need to arbitrarily
define typical compositions. Methanol and ethanol are assumed to be pure neat
alcohols, sometimes referred to as M100 and E100, respectively.
The basic thermodynamic properties of pure compounds (e.g., the critical temperature
and pressure of hydrogen or methane) are usually measured and reported with high
accuracy. Different literature sources often cite significantly different values of other
properties such as flammability limits or minimum ignition energy. This is because
subtle differences among the experiments produced these measurements.
A final fuel property comparison challenge arises for fuels such as hydrogen and natural
gas that are commonly stored at different conditions, such as compressed or liquefied.
Properties that are mass-based (e.g., lower heating value or LHV) are unaffected, but
other properties including density obviously depend on the storage condition. For
hydrogen and natural gas, Table 5-1 includes density and LHV x density (e.g., heating
value per unit storage volume) for typical compressed and liquefied storage conditions.
5
-
3
Table 5-1. Properties of Hydrogen and Other Current and Potential Automotive Fuels
25
Fuel Units Hydrogen
Natural Gas
(methane
2
)
LPG
(propane
3
) Methanol Ethanol Gasoline
4
Diesel Fuel
5
Chemical composition H2 CH4 C3H8 CH3OH C2H5OH Hydrocarbon
mixture
Hydrocarbon
mixture
Molecular weight 2.016 16.04 44.09 32.04 46.07 ~105 avg. ~200 avg.
Carbon hydrogen ratio (atom ratio) 0 0.25 0.375 0.25 0.333 0.54 0.56
Critical temperature C -240 -82 97 240 243
Critical pressure kPa 1,290 4,600 4,250 7,970 6,390
Phase at NPT gas gas gas liquid
6
liquid
6
liquid
6
liquid
6
Density at NPT kg/m
3
0.080 0.680 1.86 795
8
/1.35
9
790
8
/1.94
9
752
8
/2.88
9
857
8
/5.50
9
Boiling temperature at 1 atm C -253 -162 -42 65 78 27-225 187-343
Reid vapor pressure (RVP) kPa N/A N/A N/A 32 15 62 0.15
Lower heating value (LHV) kJ /kg 120,000 50,000 46,300 20,000 27,000 44,000 42,600
Octane rating
7
(ambiguous) 120 105 100 100 86-94 low
Cetane rating low low low low low low 40-55
Heat of vaporization kJ /kg 446 509 448 1,170 921 340 260
Stoichiometric combustion in air air/fuel
volume ratio
2.4 9.5 23.8 7.2 14.3 55 85
Flame temperature
1
C 2,045 1,877 1,980 1,871 1,920 2,027 1,993
Lower flammability unit (LFL) vol. % in air 4.1
10
5.0 2.2 6.6 3.3 1.4 0.6
Upper flammability limit (UFL) vol. % in air 75 15 9.5 37 19 7.6 6
Flash point C N/A N/A N/A 11 13 -43 70
Minimum ignition energy MJ 0.02 0.29 0.25 0.14 0.20 0.24 0.30
Autoignition temperature C 575 540 480 450 380 260 280
Burning velocity at NPT
1
m/sec 3.0 0.36 0.40 0.46 0.35
Diffusion coefficient at NPT cm
2
/sec 0.61 0.16 0.14 0.10 0.06 0.05
Flame visibility in sunlight none medium medium low low high high
Odor none None
12
none
12
yes yes yes yes
Taste none none none none
13
none
13
yes yes
Toxicity none
11
None
11
none
11
posionous
13
intoxicating
13
yes
14
yes
14
Typical vehicle storage modes
Compressed (CH2)
15
Liquefied (LH2)
16
Compressed (CNG)
17
Liquefied (LNG)
12
Compressed
19
Liquid at
ambient P&T
Liquid at
ambient P&T
Liquid at
ambient P&T
Liquid at
ambient P&T
Density for typical storage
modes
kg/m
3
kg/m
3
CH2: 23.8
20
LH2: 66.6
21
CNG: 205
22
LNG: 384
23
508
24
795 790 752 857
LHV x density for typical storage
modes
MJ /m
3
MJ /m
3
CH2: 2,760
20
LH2: 7,990
21
CNG: 10,250
22
LNG: 19,200
23
23,520
24
15,900 21,330 33,100 36,500
5
-
4
Notes to Table 5-1
1. Properties of stoichiometric fuel-air mixture.
2. Natural gas is a mixture of methane plus small but variable amounts of other light hydrocarbons, nitrogen, carbon dioxide, water vapor, and other gases. Natural gas is
characterized here as 100% methane in order to provide unambiguous properties.
3. LPG (liquid petroleum gas) used as a motor vehicle fuel is usually consistent with specifications that limit the concentrations of non-propane constituents such as butane
and propylene. LPG is characterized here as 100% propane in order to provide unambiguous properties.
4. Gasoline is a mixture of hydrocarbons plus small quantities of other constituents with variable compositions depending on location, season, prevailing regulations, and
refiner. Properties shown are approximately typical averages or ranges.
5. Diesel fuel a mixture of hydrocarbons plus small quantities of other constituents with variable compositions depending on location, season, prevailing regulations, and
refiner. Properties shown are approximately typical averages or ranges.
6. Liquid with low vapor pressure; see density and RVP properties.
7. Octane rating shown =(Research Octane No. +Motor Octane No.)/2. Note that there is ambiguity with respect to octane rating definitions when octane rating >100, and so
these values should be regarded as very approximate.
8. Liquid density at NPT =15.5C (60F) and 101.56 kPa (14.73 psi), as defined by American Gas Association.
9. Approximate density of fuel vapors saturated at NPT.
10. Recent tests indicate that hydrogens LFL is 4.1% only under special circumstances, and it is somewhat higher in most practical situations.
11. These gaseous fuels are nontoxic, but they can cause asphyxiation if their concentration is high enough to displace significant oxygen.
12. Odorants are added to natural gas and LPG in many applications so that leaks are detectable by smell.
13. Taste deterrents (denaturants) are often added to methanol because of its toxicity and to ethanol to ensure that alcoholic beverages are appropriately taxed.
14. Some gasoline and diesel fuel components are carcinogenic.
15. Compressed hydrogen is typically stored at 24.8 MPa (3,600 psi) or 34.5 Mpa (5,000 psi).
16. Liquid hydrogen is typically stored saturated at 250C (-418F).
17. CNG is typically stored at 20.7 MPa (3,000 psi) or 24.8 MPa (3,600 psi).
18. LNG is typically stored saturated at 134C (-210F).
19. Propane liquefies when compressed at ambient temperatures and is typically stored saturated at 0.63 MPa (92 psig) and 15.6C (60F).
20. At 34.5 MPa (6,000 psi).
21. At 250C (-418F).
22. At 24.8 MPa (3,600 psi).
23. At 134C (-210F).
24. Saturated at 15.6C (60F).
25. Data sources: DOE AFDC, Kirk, NASA 1997, Murphy, Browning, AGA 1981, Perry, and Peschka
5-5
5.3 Fuel Property Comparisons and Implications
This section highlights a few of hydrogens unique properties that affect risk and safety
issues when it is used as an automotive fuel. Section 5.4 makes a direct comparison of
hydrogen with natural gas and Section 5.5 summarizes some general ways in which
hydrogen may be more or less safe than other automotive fuels.
5.3.1 Properties Affecting Leakage
Because hydrogen is stored at high pressures or cryogenic temperatures, and because
the hydrogen molecule is so small, hydrogen is more leak prone than other fuels.
Hydrogen can leak through air-tight seals and escape from systems that have tested
leak-free with gases such as nitrogen (Rosen).
While hydrogens low molecular weight makes it more leak-prone, its exceptionally high
sound speed and low viscosity cause hydrogen leaks through a given-size opening to
have a much higher velocity and volumetric flow rate relative to other gaseous or liquid
fuels
8
. However, because of hydrogens low density, the mass flow rate of hydrogen
through a given-size leak opening will be less than that of other fuels.
5.3.2 Buoyancy
Because of its low critical temperature and low molecular weight, hydrogen is a gas
when warmer than 253C at atmospheric pressure, and is less dense than any other
gas at the same temperature and pressure. Therefore, hydrogen is highly buoyant.
Figure 5-1 shows hydrogens buoyancy (defined here as simply 1/density) compared
with other fuels listed in Table 5-1 and also compared to air buoyancy.
Hydrogens extraordinary buoyancy has substantial safety implications. Hydrogen rises
very rapidly. Even when considering hydrogens high diffusion coefficient, hydrogen
plumes do not spread horizontally very far (e.g., compared with natural gas or propane)
before the concentration decreases below LFL. This is because the vertical movement
and mixing is so rapid. In many outside vehicle situations, hydrogens buoyancy makes
it a relatively safe fuel; however, hydrogen leaks inside enclosed structures with
overhead ignition sources are dangerous.
8
The flow velocity of leaks induced by a high pressure differential so that the flow is choked depends on
the fluid sonic velocity. The flow velocity of leaks induced by low pressure differentials depends on the
fluid viscosity.
5-6
0
2
4
6
8
10
12
14
0 50 100 150 200
Molecular Weight
B
u
o
y
a
n
c
y

(

m
3
/
k
g

)
Hydrogen
Natural Gas
Propane
Ethanol*
Methanol*
Gasoline*
Diesel Fuel*
Air
Buoyancy =1 / Density at NPT ( 101.6 kPa & 15.5
o
C )
* Saturated vapor bouyancy for fuels that are liquids at NPT
Figure 5-1. Hydrogen is Substantially More Buoyant than Air and Other
Current and Potential Automotive Fuels
Leaked liquid hydrogen disperses relatively quickly. While liquid hydrogen is heavier
than air, hydrogen vapor becomes more buoyant than ambient air at about 250C. This
compares to natural gas, which becomes more buoyant than air at about 107C
9
. As a
result, large LNG spills are much more prone to forming dangerous ground-hugging
clouds than equivalent-quantity liquid hydrogen spills. NASA reported that spills of 500
gallons of liquid hydrogen in an unconfined area will diffuse to a nonexplosive mixture
concentration in about one minute (Rosen).
5.3.3 Flammability Limits and Ignition Energy
Table 5-1 indicates that hydrogen has relatively wide flammability limits in air, which are
usually cited in the literature as approximately four percent (LFL) to 75 percent (UFL);
however, flammability and explosive limits are highly dependent on pressure,
temperature, and diluents, and especially on the details of the hydrogen-air mixture and
ignition source interaction. For example, recent experiments at the University of Miami
have shown that, while a strong ignition source can produce a small upward-
propagating pencil of flame in a 4.1 percent hydrogen-in-air mixture, all of the
hydrogen is not combusted until the concentration reaches about 10 percent (Swain).
9
The buoyancy of a cryogenic gas plume is also affected by mixing with and heat transfer to the
surrounding air.
5-7
The energy required to ignite a near stoichiometric hydrogen-air mixture is extremely
low, (usually cited as 0.02 mJ ), but it increases near the flammability limits. There are
many literature accounts (e.g., Zalosh) of accidental hydrogen leaks igniting for no
apparent reason. It is usually assumed that these were caused by small static electricity
discharges. Interestingly, while hydrogens minimum ignition energy is quite low, its
autoignition temperature (approximately 575C) is the highest of any of the fuels listed
in Table 5-1.
Hydrogens wide flammability limits and low ignition energy can actually enhance safety
in certain situations. For example, if a small leak ignites immediately, in some cases a
small diffusion flame will form that does not ignite or damage any nearby materials. If
such a leak is in an enclosure and does not ignite immediately, a large-volume
flammable mixture may accumulate so subsequent ignition results in substantial energy
release and damage.
5.3.4 Burning Velocity
Combustion of a premixed volume of fuel in air can occur as a deflagration or
detonation. While a precise definition of these terms is beyond the scope of this review
(see e.g., Strehlow), the flame front propagation is subsonic for a deflagration and
supersonic for a detonation. While both forms of combustion are often regarded as an
explosion, only detonations produce the overpressures associated with a shock wave.
Hydrogens high burning velocity in air makes deflagrations more dangerous, and it
makes always-dangerous detonations more probable (e.g., compared to methane-air
combustion). Danger in this context refers to damage potential. Higher burning
velocities produce rapid pressure rises, which limit the effectiveness of damage-control
means such as explosion venting (e.g., blow-out panels).
Depending on the mixture ratio, mixture volume, ignition source, and especially the
degree of confinement, hydrogen-air burning can proceed as a deflagration, detonation,
or deflagration that progresses to a detonation. In a confined space, a hydrogen-air
deflagration can increase the pressure by a factor of about seven, but a detonation can
increase the pressure by a factor of about 20 (Rosen). In summary, compared with most
other fuels, hydrogen-air mixtures are much more easily ignited, and ignited mixtures
are more likely to develop into detonations.
5.3.5 Heating Value
Hydrogen has a higher heating value per unit mass (LHV =120,000 kJ /kg) than any
other candidate automotive fuel. Yet, because hydrogens density is so low, it has a
relatively low heating value per unit volume at atmospheric pressure when compressed
and liquefied. This is why it is challenging to store hydrogen in motor vehicles.
5-8
In many situations, the volume of air or fuel-air mixture is the limiting factor. This is the
case for internal combustion engines where power is limited by air processing capacity
and not fuel processing capacity. This is also the case for most accidental deflagrations
or detonations. Consider the simplified example of fuel leaking slowly into an enclosed
structure, so that the concentration is essentially uniform within the structure at one
atmosphere (i.e., the time scale is such that the gas has diffused and mixed so that
concentration gradients are negligible). If there is a constant ignition source inside the
structure, combustion will start when the mixture reaches the lower flammability limit
(LFL), and the energy release will be the product of the fuel volumetric heating value
times LFL times structure volume. The maximum energy release corresponding to this
hypothetical case occurs when the mixture ignites just as it reaches its stoichiometric
ratio. If ignition occurs when the mixture is richer, less energy is released. This is
because there is inadequate air to react with the fuel, but the excess fuel could burn
subsequently if it mixes with air outside the collapsed structure.
Table 5-2 compares the energy released in a hypothetical 85-m
3
(3,000-ft
3
) residential
garage with fully mixed hydrogen or methane at their respective LFLs and stoichiometric
ratios.
Table 5-2. Energy Release Following Ignition of Hypothetical
Uniform Fuel-Air Mixtures in an 85-m
3
Garage
Energy Released (kJ) for:
Hydrogen Methane
If ignition at LFL 33 145
If ignition at stoichiometric 240 275
5.3.6 Detectability
While hydrogen is relatively leak prone, hydrogen leaks and flames are both difficult to
detect. Hydrogen leak detectors can be based on principles such as catalytic
combustion, absorption in hydrides such as palladium (which produces a temperature
rise), hydrogens very high thermal conductivity, or the difference between hydrogens
and airs index of refraction. The challenge associated with many of these leak
detectors is the possibility that they themselves could become an ignition source, and
this is exacerbated by hydrogens low ignition energy and wide flammability limits. There
are documented accounts of explosions caused by air-sampling equipment used by
personnel who were trying to determine if there was a hydrogen leak (Zalosh).
Hydrogen, methane, and propane are essentially odorless. Odorants, typically
mercaptans, are often added to natural gas and LPG so that leaks can be detected by
their smell. However, it is impractical to odorize hydrogen automotive fuels with these
5-9
compounds because even very small sulfur concentrations found in these odorants
poison fuel cells.
The invisibility of hydrogen flames has been a factor in documented accidents. For
example, Zalosh reports on an accident where a hydrogen and hydrocarbon mixture
was leaking from a chemical processing heat exchanger. The leak ignited and produced
a two foot-long torch flame. The flame appeared to go out when the hydrocarbon flow
was turned off. However, as was later learned, the flame simply became invisible and
proceeded to melt a 12-foot-long section of the heat exchanger.
Hydrogen flames produce no significant continuum or visible radiation. What little
energy is radiated is contained in narrow UV or IR bands that derive from OH and H
2
O.
The total energy radiated by hydrogen flames is about an order of magnitude less than
that from most other hydrocarbon flames. This makes them very challenging to detect
by optical methods; however, this also means that the radiation heat transfer injury or
damage from hydrogen fires is much less than that from gasoline or diesel fires.
5.3.7 Quenching Distance
Flame arrestors, which stop flames from propagating, are used on components such as
vent stack and electrical enclosures at facilities that flow flammable gases. These
devices usually have small openings, typically created by fine-mesh screens, that
quench the flame. The size of the opening that quenches the flame, which is called the
quenching distance, depends on the gas and its concentration and pressure.
Hydrogen has an unusually small quenching distance. At one atmosphere, the
quenching distance is about 0.06 cm for hydrogen compared to 0.2 cm for propane. The
practical safety implications suggest that many flame arrestors suitable for hydrocarbon
fuels are unsuitable for use with hydrogen.
5.3.8 Liquid Hydrogen Properties
Liquid hydrogen involves some special risk and safety issues. Large quantities of spilled
liquid hydrogen can pool and produce a ground-hugging cold vapor cloud, But as
discussed in Section 5.3.2, the liquid evaporates and the cloud diffuses very quickly
(e.g., compared to LNG). Any liquid hydrogen uninsulated plumbing or transfer
operations present the potential for cryogenic burns. However, the frost and water vapor
clouds that naturally form in these areas usually alert personnel to the cold
temperatures.
One notable risk results from the fact that hydrogens liquefaction temperature (-253C
at 1 atm) is substantially less than the liquefaction temperature of air (-194C at 1 atm).
Uninsulated plumbing containing hydrogen liquid or cold vapor can liquefy the
surrounding air. Because oxygen has a higher liquefaction temperature than nitrogen,
the liquid is highly enriched in oxygen. An explosive mixture can result if this enriched
5-10
liquid air drips on combustible materials such as asphalt (NASA 1997). This is not an
issue with LNG, which is warmer than the air liquefaction temperature.
5.4 Hydrogen Compared to Natural Gas
The relative safety of using hydrogen and natural gas as automotive fuels is of particular
interest because:
Both hydrogen and natural gas are lighter-than-air gases
Both fuels are commonly stored as a compressed gas or cryogenic liquid
There is some substantial experience with CNG and LNG vehicles and fueling
stations, but there is less experience with compressed and liquid hydrogen vehicles
and stations
There is also discussion within the hydrogen community regarding hydrogen vehicle
and fueling station safety codes and standards. Should they be developed by modifying
existing natural gas vehicle (NGV) and station codes and standards, or by modifying
existing codes and standards for industrial (non-vehicle) hydrogen facilities? For
example, a comparison of NGV and hydrogen fueling applications (Campbell) asserts
that hydrogen properties and safety requirements are quite different than those for
natural gas. Another study, which does not focus on vehicle applications (Zalosh),
states, It is particularly useful to discuss hydrogen safety in comparison to our existing
natural gas safety experience.
The relative safety issues pertaining to hydrogen and natural gas use as an automotive
fuel and how these are related to the fuels properties are subsets of the discussion in
Section 5.3 and the properties listed in Table 5-1. Table 5-3 summarizes the main
implications of differences between key hydrogen and natural gas properties with
respect to vehicle and fueling station safety.
5.5 Hydrogen Leak, Fire, and Explosion Risk Summary
As explained in Section 5.1, hydrogen may be more or less safe than other candidate
automotive fuels, depending on the specific situation. There are many situations where
hydrogen is safer than most other fuels. For example, hydrogen itself is nontoxic, while
some other fuels are highly toxic. Hydrogen exhaust is harmless, while the exhaust from
all other fuels contain toxic CO and the exhaust from some fuels is carcinogenic.
However, situations that might involve leaks, fires, and explosions are of high interest
for all fuels. The relative risk and safety of hydrogen in these situations depend on the
specific details of the scenario. Table 5-4 summarizes the key properties and
characteristics of hydrogen that can make it more prone or less prone to leaks, fires,
explosions, and resultant damage or injury relative to other fuels.
5-11
Table 5-3. Summary Comparison of Key Hydrogen and Natural Gas Safety
Implications
Properties
a
Hydrogen
Natural Gas
(Methane) Implications
Molecular weight
Density at NPT
Diffusion Coef. at NPT
LFL-UFL in air
Min. Ign. Energy
Boiling temp. at 1 atm
Heat of vap. at 1 atm
Volumetric LHV
b
Burning velocity
Leak detectability
Flame detectability
2.016
0.08 kg/m
3
0.61 cm
2
/sec
4.1-75% Vol.
0.02 mJ
-253C
446 kJ /kg
9,600 kJ / m
3
3.0 m/sec
low
low
16.04
0.68 kg/m
3
0.16 cm
2
/sec
5.0-15% Vol.
0.29 mJ
-162C
509 kJ /kg
34,000 kJ / m
3
0.36 m/sec
low
medium
Hydrogen is more leak prone
Hydrogen leaks are substantially more
buoyant and they diffuse faster, which
causes concentration to drop below LFL
more quickly.
Confined hydrogen leaks into air are more
likely to ignite
Liquid hydrogen spills dissipate to less-
than-LFL more quickly than LNG spills
Hydrogen-air combustion energy release
in a confined volume is less
Ignited hydrogen-air mixtures are more
likely to detonate
Both hydrogen and natural gas leaks are
difficult to detect unless gas is odorized
Hydrogen flames are more difficult to see
or detect with instruments
a
See Table 5-1 for additional details.
b
At LFL, 1 atm, 15C
5-12
Table 5-4. Hydrogen Properties and Characteristics That Make it More Prone or
Less Prone to Leaks, Fires, and Explosions Relative to Other Fuels
Properties and Characteristics That Make
Hydrogen More Prone to Leaks, Fires,
and Explosions Relative to Other Fuels
Properties and Characteristics That Make
Hydrogen Less Prone to Leaks, Fires,
and Explosions Relative to Other Fuels
Hydrogen is usually stored at very high
pressures or low temperatures, both of
which increase the potential for leaks.
The hydrogen molecules small size
permits it to leak through air-tight seals.
Hydrogens high sound speed and low
viscosity result in a high volumetric leak
rate.
Hydrogen leaks are relatively difficult to
detect (by either human senses or
sensors)
Hydrogen leaks rise (like methane), so it
can collect and form combustible
mixtures in indoor areas such as non-
ventilated ceilings.
Hydrogens wide flammability range in air
and its exceptionally low ignition energy
requirement make hydrogen leaks
relatively ignition prone.
Hydrogens high flame speed in air
makes these mixtures relatively
detonation prone. Deflagrations can
progress to detonations in some cases.
Hydrogen flames are relatively difficult to
detect (by either human vision or
sensors)
Hydrogens relatively small quenching
distance make flame arrestor design
more challenging (e.g., some flame
arrestors that are effective for other fuels
are not effective for hydrogen).
Hydrogens low density makes hydrogen leaks
extremely buoyant. The rapid upward flow and
mixing of hydrogen leaks in open areas results in
a relatively small combustible volume. Fuels that
leak down (e.g., gasoline, diesel fuel, alcohols,
propane) can spread over the ground and engulf
large areas in long-duration flames when they are
ignited.
Hydrogens high rate of diffusion in air causes
hydrogen releases to diffuse to less-than-
flammable concentrations more quickly than
other fuels.
Hydrogens low ignition energy and wide
flammability limits can cause hydrogen leaks to
ignite immediately and burn as a small steady
diffusion flame so that large volumes of
combustible mixtures do not accumulate and
ignite subsequently.
If hydrogen-air mixtures do accumulate and
ignition occurs when the mixture reaches LFL,
the resulting energy release and damage
potential will be less than with other fuels (due
primarily to hydrogens low density).
Fuels such as diesel fuel and gasoline radiate
substantial energy when they burn, which makes
these fires more likely to damage or ignite nearby
objects or injure humans. Hydrogen fires radiate
much less thermal energy.
Because hydrogen fuel cell vehicles are more
efficient than internal combustion engine vehicles
that use other fuels, they will carry less fuel
energy that can be released in case of an
accident.
6-1
6. CONCLUSIONS
Objective and Approach Summary
A variety of strategies and fueling station design options are being considered for the
current expansion of hydrogen infrastructure. Because there is very little operating
experience with any of these, the safety issues are poorly understood. This study
identified key safety issues pertaining to four types of hydrogen fueling stations and one
type of natural gas fueling station:
Liquid hydrogen delivery
Electrolysis onsite production
Steam methane reforming onsite production
Compressed hydrogen (tube trailer) delivery
Conventional compressed natural gas (CNG) station
The key safety issues were identified by defining representative generic designs for
these stations and then conducting a top-level FMEA for each type of station. The
generic station design definitions included top-level process flow diagrams, P&IDs,
equipment specifications, operating procedures, and lists of applicable codes and
standards. The FMEA panel included experts in pertinent technical fields and the FMEA
process.
Standard FMEA forms were completed for each station design option. These listed the
potential failure modes and their causes, effects, and controls. In keeping with the top-
level analysis approach, the frequencies and consequences of potential failures were
rated in terms of a defined high, medium, and low scale. The FMEA results for each
type of station were analyzed by constructing a risk-binning matrix, which summarized
the numbers of each of the nine frequency-consequence combinations (i.e., from low-
low to high-high).
A general assessment of hydrogen safety issues, which was independent of specific
station designs, was also carried out. This assessment was based on a detailed
analysis of hydrogens physical and chemical properties. It compared hydrogen safety
issues to those of other fuels in general and natural gas in particular.
General Station Safety Conclusions
The overarching risk associated with all five types of stations is the potential for a gas
release and ignition. Gas releases range from small leaks, for which there are more
opportunities, but the consequences are not always severe, to significant discharges
(e.g., tank rupture). Many potential sources of gas releases are common to all the types
of stations considered. For example, various potential leaks associated with the
dispenser including connected drive-away scenarios are rated low-medium or medium-
6-2
low in terms of frequency-consequence. On the other hand, various potential failures
associated with pressure vessel cascades, most of which result in a substantial release
of high-pressure gas, are rated low frequency and high consequence. There are many
opportunities for compressor failures that produce leaks, and most of these are rated
low frequency and medium consequence.
Specific Station Safety Conclusions
While the dispenser, high-pressure vessel, and compressor components of all the
considered station designs are similar, the hydrogen production or delivery and storage
components are quite different. Potentially serious failure modes associated with liquid
hydrogen delivery and storage include accidental overfilling so as to cause liquid
venting (rated high frequency and medium consequence), collisions of the cryogenic
tank truck (rated medium frequency and medium consequence), and substantial PSV
venting if the storage tank vacuum is lost (rated medium frequency and medium
consequence).
Many potential failure modes are associated with an onsite electrolyzer and its related
components. These could result in leaks of hydrogen, oxygen, or KOH, and they could
also expose personnel to high voltages. However, all of these are rated low in terms of
frequency, although some are rated high in terms of consequence.
The only medium-frequency electrolyzer failure involves a dryer malfunction that allows
moisture to enter downstream components, and the consequence is rated low because
it would probably be detected right away. The component associated with onsite
reforming also provides many opportunities for failures that are rated low frequency and
medium or high consequence. The only potential failure with a medium frequency rating
is a condensate separator malfunction that might produce a fire or explosion, which is
given a medium consequence rating. While use of a tube trailer provides relatively few
failure opportunities, some of these failures, such as a leak resulting from an impact
during change out are given medium frequency and medium consequence ratings. Also,
while a tube rupture is a very low frequency possibility, it is certainly a high
consequence event.
Factors such as pipeline delivery, natural gas properties, and more experience combine
to give conventional CNG stations relatively few failure modes with a high consequence,
and all of these are rated as being low frequency.
Hydrogen Safety Relative to Other Fuels
Hydrogen is safer than other fuels in some scenarios and it is less safe in other
scenarios. There is not yet enough experience to draw conclusions regarding hydrogen
vehicle safety from statistics, and so we can only make projections based on hydrogen
6-3
properties. A detailed quantitative comparison of 29 hydrogen properties with those of
six other liquid and gaseous fuels was carried out.
Hydrogen is extremely buoyant, and this makes it safer than fuels that are heavier than
air (e.g., gasoline, propane) in many leak and other accidental release situations. On
the other hand, hydrogen is relatively leak prone, particularly considering the fact that it
is usually stored at high pressures, flammable mixtures are easily ignited, and it is
difficult to detect. These characteristics may make hydrogen less safe than other fuels
in some accident scenarios. While hydrogens industrial-use safety record is good, this
application does not include all vehicle fuel and lay person issues. Fortunately, safety
research is underway and codes and standards are being developed to address
hydrogen vehicle fuel applications.
R-1
REFERENCES
Lawrence Livermore National Laboratory, Environment, Safety, and Health Manual,
Volume I; Part 3: Safety Analysis and Work Plans and Procedures; UCRL-AM-133867,
Editorial Update: September 23, 2004 www.llnl.gov/es_and_h/hsm/doc_3.01/doc3-
01.pdf
AGA, AGA LNG Information Book 1981, American Gas Association Catalog Number
X00G81, 1981.
Arthur D. Little, (ADL), Comparative Risk Assessment of Gasoline, Propane, and NGV
Fueling and Conversion Repair Facilities, Report to the (Canadian) Government-
Industry Committee on the Siting of Propane and Natural Gas Trans Fuel Facilities, May
1991.
Browning, L., et al., Development of a Universal Methanol Fuel Formulation for Use in
Both Light- and Heavy-Duty Vehicles, Phase I Risk Assessment, Acurex
Environmental Final Report 96-115 for NREL, November 1996.
Campbell, K. and Cohen, J ., Why Hydrogen Vehicle Fueling is Different than Natural
Gas, presented at the World NGV 2002 8th International and 20th National Conference
and Exhibition, Washington, D.C., October, 2002.
California Air Resources Board (ARB 1999a), Staff Report: Initial Statement of
Reasons, Proposed Regulation for a Public Transit Bus Fleet Rule and Emission
Standards for New Urban Buses, December 1999. Also see
www.arb.ca.gov/regact/bus/bus.htm
California Air Resources Board (ARB 1999b), California Exhaust Emission Standards
and Test Procedures for 2003 and Subsequent Model Zero-Emission Vehicles, and
2001 and Subsequent Model Hybrid Electric Vehicles in the Passenger Car, Light-Duty
Truck and Medium Duty Vehicle Classes, December 1999.
DOE AFDC - U.S. Department of Energy Alternative Fuels Data Center:
www.afdc.doe.gov/altfuels.html
California Hydrogen Highway Network Website:
www.hydrogenhighway.ca.gov/announce/announce.htm
Kirk - Othmer Encyclopedia of Chemical Engineering, Alcohol Fuels, Volume 11, 3rd
Ed., 1984.
California Legislature website, www.leginfo.ca.gov/pub/bill/asm/ab_0701-
0750/ab_740_bill_20030410_amended_asm.pdf
R-2
McDermott, R. The Basics of FMEA, Productivity Inc. Portland OR, 1996.
Murphy, M. J ., Properties of Alternative Fuels, DOT UMPTA-OH-06-0056-91-9, Dec.,
1991.
NASA 1997, Safety Standard for Hydrogen and Hydrogen Systems, NASA NSS
1740.16, Feb., 1997.
Perry, Chemical Engineers Handbook, Fifth Edition, McGraw-Hill, New York, 1973.
Peschka, W., Liquid Hydrogen, Fuel of the Future, Springer-Verlag/Wein, New York,
1992.
Powars, C., TIAX LLC, California Hydrogen Fueling Station Guidelines, Consultant
Report for the California Energy Commission, #600-04-002V1, November 2004.
Rosen, B., Dayen, V., and Proffit, R., Hydrogen Leak and Fire Detection, NASA SP-
5092, 1970.
Stamatis, D.H., Failure Mode and Effect Analysis, FMEA Theory and Execution,
American Society for Quality, ASQ Press, 1995.
Strehlow, R. A., Fundamentals of Combustion, International Textbook Co., Scranton,
PA, 1968.
Swain, M., Codes and Standards Analysis, presented at the Hydrogen Fuel Cells &
Infrastructure Technologies Program 2003 Merit Review and Peer Evaluation Meeting,
Berkeley, CA, May, 2003.
U.S. Department of Energy (DOE 2003a), Guidance for Safety Aspects of Proposed
Hydrogen Projects, Hydrogen, Fuel Cells & Infrastructure Technologies Program, J uly
2003
U.S. Department of Energy (DOE 2003b), Hydrogen Fuel Cells, Infrastructure
Technologies, Section VIB.
Zalosh, R., and Short, T., Compilation and Analysis of Hydrogen Accident Reports,
Factory Mutual Research Corp., Final Report C00-4492-4 for DOE, October, 1978.

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C

Seal failure Mechanical failure Release of hydrogen and

Fill storage tank on

Use wrong pressure

Hydrogen gas leak Mechanical failure and

Catalytic purifier failure Fouling (may also

Seal failure Mechanical failure Release of hydrogen and

High pressure (6,250

Overpressure and fail

Use wrong pressure

Seal failure Mechanical failure Release of hydrogen and

Fill storage tank on

Use wrong pressure

Seal failure Mechanical failure Release of hydrogen and

High pressure (6,250

Use wrong pressure

Natural gas dryer

Relief device failure

Use wrong pressure

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