Adsorbed Natural Gas Fuel System

Requirements Specification Document

ARPA-E DE-AR0000251

12/31/14
Version 1.0

Revision History
Note: The revision history cycle begins once changes or enhancements are requested after the
Requirements Specification Document has been issued.
Date

Version

Description

Author

12/31/14

1.0

Initial published release

M. Veenstra

Artifact Rationale
The Requirements Specification Document (RSD) records the results of the specification
gathering processes carried out during the requirements phase of ARPA-E project award DEAR0000251. The RSD is generally written to provide the bulk of the information required to
develop the essential properties necessary for a competitive system. It may be updated within
the project based on the development of reference material and system engineering.

Adsorbed Natural Gas Fuel System

Requirements Specification Document

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Table of Contents

1.

Introduction ........................................................................................ 3
1.1. Purpose ............................................................................................................ 3
1.2. Scope ................................................................................................................ 3
1.3. References ....................................................................................................... 3

2.

Overall Requirements ........................................................................ 4

2.1.
2.2.
2.3.
2.4.
2.5.
2.6.

3.

Volumetric and Gravimetric Energy Density ................................................. 5

Storage System Cost ....................................................................................... 5
Durability/Operability....................................................................................... 6
Charging / Discharging Rates ......................................................................... 6
Fuel Quality ...................................................................................................... 6
Environmental Health & Safety ....................................................................... 6

Material Data Requirements .............................................................. 7

3.1. Isotherms of excess adsorption ..................................................................... 7
3.2. Crystal Density ................................................................................................. 7
3.3. Pore Volume ..................................................................................................... 7
3.4. Bulk Powder Tap Density ................................................................................ 8
3.5. Surface Area ..................................................................................................... 8
3.6. Skeletal Density ............................................................................................... 8
3.7. Specific Heat .................................................................................................... 8
3.8. Thermal conductivity of compact ................................................................... 8
3.9. Thermal Stability .............................................................................................. 8
3.10.Chemical Stability ............................................................................................ 8
3.11.Precursors, solvents, and activation conditions .......................................... 8
3.12.Densified media ............................................................................................... 8

Appendix I ANG System Projections .................................................... 9

Appendix II Natural Gas Fuel Quality ................................................. 10

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1. Introduction
This Requirements Specification Document (RSD) contains the parameters for the Adsorbed
Natural Gas (ANG) fuel system. Ford Motor Company (Ford) together with University of
California-Berkeley (UCB), Savannah River National Laboratory (SRNL), and BASF are
involved in a collaborative ARPA-E project (DE-AR0000251) to develop an innovative
approach for a low-pressure ANG fuel system. To this end, the project involves quantifying
performance parameters to establish the targets on a system level along with the needed key
material properties for a viable system design.

1.1. Purpose
The purpose of this document is to communicate the system requirements of the ANG fuel
system in order to develop the technology as a competitive option for natural gas vehicles. The
ANG fuel system must ultimately provide the customers with the safety, robustness,
performance, convenience, and price that they expect from an automotive compressed natural
gas fuel system.

1.2. Scope
Traditional compressed natural gas fuel systems attempt to compensate for low energy density
and limited driving range by storing compressed gas at high pressures, requiring expensive and
cylindrical pressure vessels. The ANG fuel system allows for a significantly more natural gas to
be stored at low pressures through the use of porous sorbent material in the tank. The key
benefit of the ANG fuel system is the reduced storage pressure which lowers the cost of the onboard tank and the cost of the fueling station compresors while facilitating novel conformable
tank concepts. The approach of this RSD is based on a disciplined system engineering method
that cascades the ANG requirements from the natural gas vehicle requirements based on the
customer expectations. The scope of the requirements in this document is to provide guidance
for ANG fuel system with competitive performance of current natural gas vehicles while
delivering the significant benefit of lower storage pressure to reduce the capital and fuel cost at
the dispensing stations.

1.3.References
[1] DE-FOA-000672: Methane Opportunities for Vehicular Energey (MOVE). Advanced
Research Projects Agency-Energy, U.S. Department of Energy, https://arpa-efoa.energy.gov/FileContent.aspx?FileID=13088dca-1cf6-4591-8cfc-ea81edfa786e
[2] N. Sirosh, Quantum Technologies. Compressed Natural Gas On-Board Storage: ARPA-E
NATURAL GAS VEHICLE TECHNOLOGIES WORKSHOP, January 26, 2012. In addition
for complete on-board system comparison, an estimated 20 kg and 10 liters was included for
complete system evaluation based on OEM input.
[3] The highest recorded ambient temperature (excluding oven effect from sun load) in the world
is 56.7C recorded at Death Valley, CA, USA in 1913. Court, A. How hot is Death Valley?
Geographical Review, 39, pp. 214-220, 1949.
[4] Ford Motor Company Qualified Vehicle Modifier Bulletin - Gaseous Fuels Unique
Guidelines and Requirements, August 16, 2012.

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2. Overall Requirements
The overall technical system targets for an ANG fuel system is provided in Table 1 developed
from a competitive cascade from the current customer expections to the vehicle requirements to
the system requirements. As a further decomposition of the requirements, the Table 1 includes
not only the system targets but also an additional cascade to the tank and sorbent material level.
The rational for each of the storage parameters are provided below in the specified subsections.
Table 1. Technical System Targets for an Adsorbed Natural Gas Fuel System
Storage Parameter

Units

Target

Level

Volumetric Energy Density:

- Useable energy density

MJ/L sorbent
MJ/L tank
MJ/L system

9.8 - 12.5
6.0 - 7.4
5.7 - 7.3

Sorbent
Tank
System

Gravimetric Energy Density:

- Useable energy density

g CH4/g sorbent
g CH4/g tank
g CH4/g system

0.5
0.3
0.2

Sorbent
Tank
System

$/kg sorbent
$/ sorbent bed
$/ tank
$/ system

10 - 30
500 - 1500
800 - 1800
1500 - 2500

Sorbent
Sorbent Bed
Tank
System

C
C
C
C
Cycles
Cycles
Initial Capacity
bar (abs)
bar (abs)

-40/60
-40/85
-40/85
-55/85
100
1000
90%
5
60

System
System
Tank (Inner)
Tank (Inner)
System
System
Sorbent
System
System

min
kg/h-L
(g/s)
s
s
s

3-5
0.2
(7.8)
10
5
3

System

mol%

See note
Meets or
exceeds
applicable
standards

Storage System Cost :

- Based on 10 GGE projected storage

Durability/Operability:
Operating ambient temperature
Min/max delivery temperature
Min/max desorption temperature
Min/max adsorption temperature
Demonstration cycle life
Operational customer cycle life
Max Degradation after cycle life
Min delivery pressure to engine
Max nominal storage pressure
Charging / Discharging Rates:
System fill time (10 GGE)
Specific desorption flow rate
Max. start time to full flow (-30 C)
Max. start time to full flow (-20 C)
Max. start time to full flow (0 C)
Fuel Quality (to/from storage):
Environmental Health & Safety:

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System
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2.1.

Volumetric and Gravimetric Energy Density

The system energy density projections are based on providing competitive performance to a 250
bar Type IV compressed natural gas (CNG) tank. The ARPA-E Ref[1] provides values for a
Type IV tank including the CNG as 7.4 MJ/L and 15.6 MJ/kg (31 wt%) energy density. The
APRA-E volumetric target for the system is based on the energy of the fuel divided by the
volume of the smallest rectangular cuboid that encloses the tank. Using this definintion from
ARPA-E and commercial Type IV tanks, the volumetric density for a Type IV tank is around 6.0
MJ/L which has been included in Table 1 to recognize the range. The ARPA-E gravimetric
energy density values were developed based on commercial tank properties from Quantum, a
CNG tank supplier, per Ref[2].
For a complete system comparison, the additional CNG system components must be included
with the tank energy density. Based on commercial CNG projections, the addition of 20 kg of
weight and 10 liters of volume for the CNG components result in the system level energy
density targets in Table 1.
Based on an assumed 10 GGE ANG storage system, the determination of the sorbent level target
can be derived by estimating the ANG system components (see Appendix I) and then subtracting
their volume and weight from the system level targets. The tank level target includes the tank,
sorbent, heat exchanger, and other additives to manage the performance of the adsorbent along
with packing losses. The remaing cascade to the sorbent material target is based on tank target
with the removal of the other items except for the sorbent. Based on various sensitivity studies,
it was estimated the tank and other assoiciated items would equate to about 45 kg of weight and
20 liters of volume. The sorbent level target includes packing losses, which has been assumed to
be 25% by ARPA-E per Ref[1] although derived sorbent level target assumes up to a 50%
volumetric density reduction to result in the target ranges in Table 1. Useable energy density is
determined based on the available density between the normal working pressure and minimum
delivery pressure at the nominal rated temperature. For CNG, the nominal rated temperature for
determining the useable energy density is 21 C.

2.2.

Storage System Cost

The on-board storage system cost target indicated in the ARPA-E Ref[1] was $1,500 in order to
facilitate the inclusion of at-home refueling unit at $500 for a total storage related cost of $2,000.
Based on commercial tank systems from Ford Qualified Vehicle Modifiers, a 10 GGE CNG
system would cost around $2,500 which is similar to the CNG tank system cost estimate
provided by Strategic Analysis of $2,300 at 50k units per year. Table 1 includes the range of
system cost.
In a similar manner as the energy density evaluation, the determination of the tank level target
can be derived by estimating the ANG system components at about $700 (see Appendix I) and
then subtracting their cost from the system level targets. The tank level target includes the tank,
sorbent, heat exchanger, and other additives to manage the performance of the adsorbent along
with packing losses. The remaing cascade to the sorbent material target is based on tank target
with the removal of the other items except for the sorbent which has been estimated at $300
based on various sensitivity studies. The final sorbent material cost assumes the material
achieves the gravimetric target of 0.5 that results in approximately 50 kg of sorbent for the 10
GGE of CNG storage.
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2.3.

Durability/Operability

The storage system must dependably store and deliver natural gas at all expected ambient
conditions. The typical automotive low temperature is -40 C (also included in Ref[1]) while the
highest ambient temperature excluding sun load and oven effects is 60 C per Ref[3]. The
delivery temperature of the natural gas was defined in Ref[1] and also aligns with the expected
automotive fuel rail temperatures. The maximum desorption temperature is referenced in Ref[1]
and the minimum temperature is aligned with the minimum delivery temperature which can be
assumed to be the lower end of the engine coolant performance. The adsorption temperature
range is based on the anticipated temperature cooling that could be accommodated during fueling
and expected to remain within the operating temperature of the tank.
Demonstration life time is based on expected cycle testing within the project duration (3 years)
while the actual customer usage life cycles is 1,000 based on the assumption of 50 fills per year
and a 20 year lifetime as indicated in Ref[1]. The maximum degradation after customer cycle
life was initially defined by ARPA-E as 80% in Ref[1]. Based on automotive customer
experience with CNG system, this value was revised to 90% in Table 1.
The minimum delivery pressure is specified as 5 bar based Ref[1] and the typical CNG injector
requirement in the US and Europe based on the Bosch NGi2. In most cases, inlet pressure used
for these injectors is around 5 to 8 bar but in some cases 10 bar is used to get enough flow rate
through it. In other parts of the world, CNG engines are non-boosted and utilize a fuel delivery
pressure of 3.5 bar. The maximum nominal storage pressure was defined as 60 bar based on the
desire to utilize a type I tank in order to optimize the system cost. The typical peak benefit of a
sorbent material over compressed natural gas is around 35 bar. As pressure increases from this
peak, the total volumetric density still increases although the benefit is reduced.

2.4.

Charging / Discharging Rates

The fill time target is specified to achieve current automotive customer experience. Currently,
gasoline vehicles are filled in about 3 to 5 minutes, with small ligh-duty vehicles taking less time
than larger vehicles based on the capacity of their fuel tanks.
Desorption flow rate needs to be provided over the entire range of useable capacity and is based
on a 150 hp engine at 30% efficiency and 47.7 kW energy content in 1 g/s of natural gas. The
150 hp is based on a compact vehicle while additional flow rate would be required for a full-size
vehicle such as 19 g/s for 365 hp. The specific discharge rate must be measured at 20% tank
capacity over 30 seconds per Ref[1]. The start time to full flow rate is another important
parameter to ensure the vehicle is operation within the desired time at various temperature. The
requirements were taken directly Ford natural gas vehicle requirements in Ref[4].

2.5.

Fuel Quality

The system must be robust to the US pipeline quality natural gas and must not provide fuel
quality that is significantly beyond this criteria to the engine. In particular, the SAE J1616 must
be met along with natural gas quality values (see Appendix IV).

2.6.

Environmental Health & Safety

The system should be tolerant of abusive conditions and physical damage without catastrophic
failure. Safe operation of the ANG system shall be achieved with respect to toxicity and stability
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per Ref[1]. At a minimum, a CNG system must meet the requirements of FMVSS 303 and 304
per Ref[4] along with the localized codes and standards. In addition, CSA standards should be
considered such as ANSI NGV2, NGV3.1, and PRD1.

3. Material Data Requirements

The sorbent material data requirements necessary to design the ANG system and components
(e.g. internal heat exchanger) to achieve the technical targes are listed in this section. This list is
in priority order with the first item, excess adsorption isotherms, by far the most critical.
Supporting information, which is also necessary, are the crystal density, pore volume, and bulk
density. These are used to determine ultimate materials volumetric and gravimetric capacities.
The thermal conductivity and specific heat items, while necessary in system design, are not
absolutely required for material-to-material comparisons. A baseline for current state-of-the-art
adsorbed natural gas materials and properties have been provided in the following publication:
http://alchemy.cchem.berkeley.edu/jeff/paper182.pdf

3.1.

Isotherms of excess adsorption

A minimum of five isotherms at temperatures evenly distributed over the range 195<T<525K.

The temperature must be kept constant to within 2 K throughout the test sequence

Test pressures should range between 5 < P < 100 bar at an incremental pressure resolution of
5 bar

The gas composition should ideally be pure methane for comparison purposes. The gas
composition should be high quality (99.999% purity)

Natural gas data will also be accepted with the gas composition detailed with species given to
the highest accuracy known

It is suggested that tests be performed in accordance with the Best Practices Guide given in
Ref. 1, which includes measuring background CH4 adsorption isotherms for empty sample
holders (or sample holders containing a nonadsorbing material) under identical experimental
conditions to confirm the adsorption instrument is producing high quality data

Statistical fits of this data should be performed to cover the entire pressure-temperature space
being considered for the adsorption systems. This requires very stable and precise measurements
as detailed above. Volumetric and gravimetric capacities should also be derived from this data
along with isosteric heats of adsorption.

3.2.

Crystal Density

Determine using diffraction techniques. Provide complete crystal structure that was used to
determine density. Note that the crystal structure should be representative of the state of the
material during CH4 adsorption (i.e. near ambient temperature and fully desolvated).

3.3.

Pore Volume

Determine using a N2 adsorption isotherm at 77 K. Specify the isotherm model or P/P0 that was
used to calculate pore volume.
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3.4.

Bulk Powder Tap Density

Determine physically on as large a sample as possible as per ASTM D7489.

3.5.

Surface Area

Determine with BET and/or Langmuir theory using a N2 adsorption isotherm at 77 K as per
ASTM D1993.

3.6.

Skeletal Density

Determine using He displacement at room temperature.

3.7.

Specific Heat

Determine through differential scanning calorimetry with CH4 for temperatures ranging from
170 K to the maximum temperature at which the material is stable as per ASTM D1269.

3.8.

Thermal conductivity of compact

Determine at room temperature using as low a density compact as possible to retain shape as per
ASTM D1952 or ASTM D1225

3.9.

Thermal Stability

Maximum temperature at which material shows initial loss in porosity over ~12 hours.

3.10.

Chemical Stability

Evaluate chemical compatibility of the material by conducting isotherm measurement after initial
exposure and multiple cycles (~100) with common natural gas impurities (either as a composite
or preferably in isolation) such as CxH2x+2, CO2, O2, H2, S, H2O, etc.

3.11.

Precursors, solvents, and activation conditions

Describe relative amounts to be used to establish a baseline for cost comparison

3.12.

Densified media

Specify if a binder is required for compacted material stability

Provide data variations (for excess adsorption, pore volume, and thermal conductivity at a
minimum) for at least 3 compaction densities between the low density necessary to retain shape
and below the crystal density. as a function of changes in density

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Appendix I ANG System Projections

ID#
ID01
ID02
ID03
ID04
ID05
ID06
ID07
ID08
ID09
ID10-a
ID10-b
ID10-c
ID11
ID12
ID13
ID14
ID15
ID16
-------------------

Name
Mass [kg] Vol [L]
Fill receptacle
0.30
0.20
Check valve
0.13
0.10
T fitting
0.10
0.10
Guard Bed
0.00
0.00
Filter
0.02
0.00
T-PRD
0.11
0.03
On-Tank Valve
2.50
1.00
Thermocouple
0.02
0.00
Pressure Sensor
0.11
0.03
Containing vessel
Internal HX
Bed material
Pressure regulator
1.09
0.41
T-PRD
0.11
0.03
3-way valve/switch
1.00
0.75
3-way valve/switch
1.00
0.75
3-way valve/switch
1.00
0.75
3-way valve/switch
1.00
0.75
Couplings
0.29
0.01
Tubing
0.60
4.50
TOTALS =
9.38
9.39

Adsorbed Natural Gas Fuel System

Requirements Specification Document

Cost [$]
$90.00
$26.46
$11.00
$0.00
$15.00
$18.29
$175.00
$5.00
$18.29

$158.14
$18.29
$31.00
$31.00
$31.00
$31.00
$44.28
$15.58
$719.33

Couplings
1
2
3
-----2
1
10
1
1
2
----------2
1
3
3
3
3
41
----------

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Appendix II Natural Gas Fuel Quality

1. SAE J1616 highlights (refer to the current standard as the official reference) for fuel composition and
quality.
Water content: The local dewpoint temperature of the fuel should be 5.6o C below the monthly lowest dry-bulb
temperature at the maximum operating cylinder pressure. The margin of 5.6o C is intended to prevent hydrate
blockage due to pressure reduction at various stages in the vehicle fuel system.
Carbon dioxide: Given that the corrosive environment is controlled via the limited water concentration, no limits
are required on the concentration of CO2 for this purpose. Rather, a limit of 3.0% CO2 by volume is recommended
to help maintain stoichiometry.
Sulfur compounds: The total content of sulfur compounds, including odorants, should be limited to 8-30 ppm by
mass to avoid excessive exhaust catalyst poisoning.
Methanol: No methanol shall be added to natural gas at the CNG refueling station. Methanol can cause corrosion
of natural gas cylinders and deterioration of fuel system components.
Oxygen: Given that the corrosive environment is controlled by the limited water concentration, no limits are
required on the concentration of oxygen for the control of corrosion. On the other hand, the oxygen level must not
produce a mixture within the flammability limits of natural gas.
Particulate and foreign matter concentration should be minimized to avoid contamination, clogging and erosion
of fuel system components. CNG fuel delivered to the vehicle should have particulate matter content equal to or
less than 5 mm (micron) in size.
Oil content: Additional data are required to determine acceptable lubricating oil levels as well as standardized test
procedures for quantifying lubricating oil content. Lubricated compressor oil levels should be monitored and
coalescing filters may be installed downstream of the compressor discharge to control oil.
Hydrocarbon dewpoint temperature: The composition of natural gas should be such that the original gaseous
storage volume will form less than 1% of a liquid condensate at the lowest ambient temperatures and gas storage
pressure between 5.5 and 8.3 MPa, at which maximum condensation occurs, depending on gas composition.
Natural gas odorant: Natural gas introduced into any CNG refueling station or vehicle shall have a distinctive odor
strong enough for its presence to be detected down to a concentration in air of not over 1/5 of the lower
flammability limit. This is approximately 1% gas-in-air volume.

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2. Natural Gas Pipeline and other quality references

1

Range
(mol %)

Typical
Analysis
(mol %)

DTE
Analysis
(mol %)

GTI
Analysis
(mol %)

CARB
Natural Gas
4
CERT SPEC

Germany:DIN
51624:2007
Fuel Spec

Methane (CH4)

87.0 - 97.0

95.0

95.5

93.4

88.0

80

Ethane (C2H6)

1.5 7.0

3.2

2.23

3.20

6.0

12

<5

Propane (C3H8)

0.1 - 1.5

0.2

0.37

0.69

3.0
C3 and higher

6.0

<1

iso Butane (C4H10)

0.01 - 0.3

0.03

0.05

0.00

--

normal Butane
(C4H10)

0.01 - 0.3

0.03

0.07

0.25

2.0

iso Pentane (C5H12)

trace - 0.04

0.01

0.03

0.00

--

normal Pentane
(C5H12)

trace - 0.04

0.01

0.02

0.10

1.0

Hexanes (C6H14) plus

trace - 0.06

0.01

0.05

0.06

0.2
C6 and higher

0.5

Nitrogen (N2)

0.2 - 5.5

1.0

0.62

1.50

1.5 4.5
(N2+CO2)

15.0
(N2+CO2)

Carbon Dioxide (CO2)

0.1 - 1.0

0.5

1.08

0.80

Oxygen (O2)

0.01 - 0.1

0.02

0.00

0.00

1.0

3.0

Hydrogen (H2)

trace - 0.02

trace

0.00

0.00

0.1

2.0

Sulfur

5.5 mg/m

Component

Water Content

16 - 32
3
mg/m

--

ARPA-E FOA
Ref[1]

<1

10 mg/kg

< 20 ppm

40 mg/kg

< 100 ppm

Union Gas Website, a major Canadian natural gas storage, transmission and distribution company
http://www.uniongas.com/about-us/about-natural-gas/Chemical-Composition-of-Natural-Gas
2
Michigan Consolidated Gas Company Laboratory Gas Analysis Report for natural gas sample at CNG fueling facility, Jan. 2010
3
Light Duty CNG Vehicle Fuel Consumption Study Topical Report, GTI Project Number 20245, April 2006
4
California Air Resource Board Specification for Compressed Natural Gas (13 CA ADC 2292.5)
(see Title 13 -> Division 3 -> Chapter 5 -> Article 3 Specifications for Alternative Motor Vehicle Fuels)

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