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Energy Sources

ISSN: 0090-8312 (Print) 1521-0510 (Online) Journal homepage: http://www.tandfonline.com/loi/ueso19

Fuel Properties of Hydrogen, Liquefied Petroleum


Gas (LPG), and Compressed Natural Gas (CNG) for
Transportation

Ayhan Demirbas

To cite this article: Ayhan Demirbas (2002) Fuel Properties of Hydrogen, Liquefied Petroleum Gas
(LPG), and Compressed Natural Gas (CNG) for Transportation, Energy Sources, 24:7, 601-610,
DOI: 10.1080/00908312.2002.11877434

To link to this article: http://dx.doi.org/10.1080/00908312.2002.11877434

Published online: 25 Apr 2017.

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Energy Sources, 24:601–610, 2002
Copyright © 2002 Taylor & Francis
0090-8312 /02 $12.00 C .00
DOI: 10.1080/0090831029008652 7

Fuel Properties of Hydrogen, LiqueŽ ed Petroleum


Gas (LPG), and Compressed Natural Gas
(CNG) for Transportation

AYHAN DEMÇIRBAŞ
P. K. 216
61035-Trabzon
Turkey

Hydrogen has been suggested as a convenient, clean-burning fuel. Hydrogen gas may
be stored as a compressed gas or as a liquid. Hydrogen has good properties as a fuel
for internal combustion engines in automobiles. Worldwide-liqueŽ ed petroleum gas
(LPG) production is limited to about 10% of total gasoline and diesel fuel consumption
and is used to a great extent for domestic and industrial purposes. Since LPG burns
cleaner with less carbon build-up and oil contamination, engine wear is reduced
and the life of some components such as rings and bearings is much longer than
with gasoline. The high octane of LPG also minimizes wear from engine knock.
Natural gas is widely available. CO2 emission of natural gas is lower than both
diesel fuel and gasoline, which makes natural gas engines favorable also in terms
of the greenhouse effect. Positive contribution of compressed natural gas (CNG) on
environmental pollution must also be considered in economical aspects.

Keywords hydrogen, LPG, CNG, fuel properties, environmental impacts

The utilization of relatively cleaner gaseous fuels like hydrogen, liqueŽ ed petroleum gas
(LPG), compressed natural gas (CNG), or liqueŽ ed natural gas (LNG) is considered for
vehicles (Shahad and Mohammed, 2000; Kuwahara et al., 2000). For gaseous fuels the
total energy stored per unit volume is less than the liquid fuels, but urban vehicles travel
on relatively short routes daily and refueling is possible if necessary (van Ling, 1992;
Heaton and van der Weide, 1993; Ergeneman et al., 1999).
Hydrogen is not a primary fuel; it must be manufactured from water with either
fossil or nonfossil energy sources (Williamson and Edeskuty, 1986; Demirbaş, 2000a).
All primary energy sources can be used in the hydrogen-producin g process (VeziroÆglu,
1975; Demirbaş, 2000b). Hydrogen has good properties as a fuel for internal combustion
engines in automobiles.
Hydrogen will play an important role in a future energy economy mainly as a storage
and transportation medium for renewable sources (Rohland et al., 1992). These are nuclear
energy, solar energy including photovoltaic electrolyzer, photoelectrocatalysis in water
splitting, photovoltaic-support fuel cell, wind energy, hydro power, geothermal energy,
and biomass energy (Bockris, 1975).

Received 9 July 2001; accepted 28 August 2001.


Address correspondence to Ayhan Demirbaş, P. K. 216, TR-61035, Trabzon, Turkey. E-mail:
ayhandemirbas@hotmail.com

601
602 A. Demirbaş

Table 1
Comparison of world energy consumption growth rates by fuel
(average annual percent growth)

1995–2020 1995–2015 1995–2010

Fuel IEO99 IEO98 IEA DRI PEL PIRA

Oil 2.6 2.1 1.9 2.0 1.9 2.0


Natural gas 4.2 3.3 2.6 2.7 2.3 2.9
Coal 2.5 2.2 2.1 2.1 2.2 2.2
Nuclear 0.3 ¡0.4 0.0 0.7 0.5 0.5
Renewable/other 2.8 2.1 2.5 — 2.0 2.1
Total 2.9 2.3 2.0 2.0 2.0 2.2

Sources: IEO99, Energy Information Administration (EIA).


IEA: International Energy Agency.
IEO: International Energy Outlook.
DRI: World Energy Service.
PEL: Petroleum Economics Ltd.
PIRA: PIRA Energy Group.

Prospects for natural gas demand worldwide remain bright, despite the impact of the
Asian economic recession on near-term development. Natural gas (NG) consumption in
the International Energy Outlook 1999 (IEO99) is somewhat increased from last year’s
outlook, and the fuel remains the fastest growing primary energy source in the forecast
period. Worldwide gas use more than doubles in the reference case projection, reaching
4.92 trillion cubic meters in 2020 from 2.32 trillion cubic meters in 1996 (IEO, 1999).
When prepared as fuel, LPG is largely propane; common uses are for powering
automotive vehicles, for cooking and heating, and sometimes for lighting in rural areas.
LiqueŽ ed petroleum gas (LPG) is an attractive fuel for internal-combustion engines be-

Table 2
Costs of thermochemical energies for selected energy carriers

US $/l gasoline-
KWh/l US $/kWh equivalent

Liquid hydrogen from bioresources 2.64 0.123 1.00


Liquid hydrogen from fossil sources 2.64 0.073 0.58
Liquid hydrogen from hydro sources 2.64 0.136 1.18
Liquid hydrogen from wind sources 2.64 0.268 2.36
Natural gas 10.20 a 0.016 0.15
LiqueŽ ed petroleum gas 9.80 0.025 0.23
Diesel oil 10.00 0.050 0.45
Gasoline 9.10 0.060 0.55
Heavy fuel oil 11.70 a 0.015 0.14
a kWh/kg

Source: ModiŽ ed from Rohland et al. (1992).


Fuel Properties of H2 , LPG, and CNG for Transportation 603

cause it burns with little air pollution and little solid residue, it does not dilute lubricants,
and it has a high octane rating. The LPG components are a gas at ambient temperatures
and pressures and liquefy under moderate pressures (0.7–1.4 MPa). For these reasons,
LPG is a convenient automotive fuel. LPG’s gaseous properties are an advantage during
the combustion process.
Natural gas is the fastest growing primary energy source in the IEO99 forecast.
Because it is a cleaner fuel than oil or coal and not as controversial as nuclear power,
gas is expected to be the fuel of choice for many countries in the future. Comparison
of world energy consumption growth rates by fuel as average annual percent growth is
shown in Table 1. Table 2 shows the costs of thermochemical energies for selected energy
carriers.
There are some additional costs resulting from the transportation of natural gas
through pipelines and compressing it at fuel stations. However, it is still possible to
consume CNG with a price comparable to that of conventional transportation fuels.
Positive contribution of CNG to environmental pollution must also be considered in
economical aspects.

Fuel Properties of Hydrogen


The combustion products of hydrogen when it is burned completely with air consist of
water, oxygen, and nitrogen. In the meantime, it has been suggested, hydrogen is too
valuable to burn. Laboratory tests conducted on internal combustion engines burning
hydrogen demonstrate good performance (Berry et al., 1996). In comparison with an
engine burning gasoline, the emission of nitrogen oxides is far less for the engine-fueled
hydrogen. The product of hydrogen combustion with air is water vapor and negligible
pollution when the peak temperature is limited. Some oxides of nitrogen (NOx ) are
formed at very high combustion temperatures (< 2300 K); fortunately, the auto ignition
temperature of hydrogen is only 858 K.
Hydrogen has good properties as a fuel for internal combustion engines in automo-
biles. Some of the characteristic properties of a hydrogen–air mixture that can deŽ nitely
in uence the engine design and performance are low ignition energy, low density, wide
range of ignition limits, high diffusion speed, and high  ame speed (Plass Jr., et al., 1990).

Storage and Transportation of Hydrogen


The main disadvantages of using hydrogen as a fuel for automobiles are huge on-board
storage tanks, which are required because of hydrogen’s extremely low density. Hydrogen
may be stored on board a vehicle as compressed gas in ultra-high-pressure vessels, as a
liquid in cryogenic containers, or as a gas bound with certain metals in metal hydrides.
The iron-titanium alloy, FeTi, acts as a sponge to absorb the hydrogen, thus becoming
a metal hydride (FeTiH1:6 ). Its physical appearance is like that of a Ž ne silvery powder.
The safest method for hydrogen storage is the “metal hydride” system (Williamson and
Edeskuty, 1986; VezirogÆ lu, 1975).
When hydrogen combines with the metal alloy (in granular form or particles), an
exothermic reaction occurs. The gas is thus stored in these metal particles until some
heat is applied to release the hydrogen and build up the pressure in the tanks. When a
metal hydride absorbs hydrogen, heat is given off. A hydride cold-start heater can be
developed that instantly heats an automobile’s catalytic converter when the car is started
to dramatically reduce overall exhaust pollution up to 80%.
604 A. Demirbaş

The 2 low-temperature hydrides, FeTiH2 and LaNi5 H7 , hold hydrogen loosely and
evolve it at low temperatures. The high-temperature hydrides, MgH and Mg2 NiH4 , only
release hydrogen at high temperatures since they have high binding enthalpies (Dinga,
1988).
The metal hydrides provide a safe method for fuel storage in hydrogen-powere d
vehicles. Charging and discharging of the hydride tanks is a process that can be re-
peated an indeŽ nite number of times provided that the hydride material does not become
contaminated.
The hydrogen would be transported from the production plant either as a gas or
in liqueŽ ed form. The liqueŽ ed hydrogen, in comparison to gaseous hydrogen, offers
the advantages of low pressure and low bulk, but containment difŽ culties arise from the
cryogenic nature of the liqueŽ ed gas.

Fuel Properties of LPG


LPG is a mixture of gases produced commercially from petroleum and stored under
pressure to keep it in a liquid state. The boiling point of LPG varies from 229 K to
273 K so that the pressure required to liquefy it is considerable and the containers for it
must be of heavy steel.
LPG is composed primarily of propane with some butane, propylene, butylene, and
other hydrocarbons, unlike gasoline, which is a complex mixture of hydrocarbons. The
composition of LPG mixes and the higher heating value of each component are given in
Table 3.
LPG’s average octane value is 104, which is higher than gasoline’s range of 84 to
97. The higher-octane value can produce signiŽ cantly better vehicle performance than
the lower octane gasoline.
LPG vapor is odorless, colorless, and heavier than air, so it will not disperse easily
without wind or ventilation. Shops servicing LPG vehicles must be ventilated to mini-
mize the risk of asphyxiation and explosions. An odorant is added to aid detection of
LPG presence. Underground parking garages should not permit parking of LPG fuelled
vehicles in their premises. LPG has a high ignition temperature, igniting at around 755 K,
compared to 533 K and 589 K for gasoline and diesel, respectively. LPG is  ammable
in concentrations between 2 and 10% in air. Gasoline is  ammable at a concentration of
1.5%. Because of LPG’s cold temperature when it changes from liquid to gas, care must
be exercised when refueling with LPG to prevent freeze burns.

Table 3
Composition of LPG mixtures and HHVs of pure substances

Component % by volume HHV (MJkg¡1 )

Propane (C3 H8 ) 60–85 50.4


Butane (C4 H10 ) 14–38 49.6
Pentane (C5 H12 ) 0–6 49.1
Isopentane (C5 H12 ) 0–0.2 49.0
Cyclopentane (C5 H12 ) 0–0.1 45.5
Ethylene (C2 H4 ) 0–1.5 49.6
Other hydrocarbons 0–2 —
Fuel Properties of H2 , LPG, and CNG for Transportation 605

Unlike gasoline, LPG is used as a dry gas and contains no fuel additives. Without lead
as a lubricating agent, some early LPG conversions resulted in increased wear rates in the
engine cylinder valves. Newer engines are designed with hardened valve seat materials.
Fuels with a high-octane value have a low cetane value, which is a measure of the ease
of a fuel to self-ignite under compression, which is important for compression-ignition
engines. LPG’s low cetane value and high octane value make it unsuitable for use in
compression-ignition engines. Since LPG burns cleaner with less carbon build-up and oil
contamination, engine wear is reduced and the life of some components such as rings
and bearings is much longer than with gasoline. The high octane of LPG also minimizes
wear from engine knock. Maintenance inspections will include checking the condition
of the ignition system, fuel system connections, storage tank mounting brackets, and
tank integrity. LPG has higher ignition temperatures than gasoline, which increases the
importance of maintaining proper ignition system operation. Improper ignition system
operation will result in improper combustion and sluggish vehicle performance. Each
conversion kit manufacturer may have speciŽ c maintenance requirements for their kit,
such as changing the fuel Ž lter.

Vehicle Operation with LPG


The LPG fuel/air mixture burns well, so engine starting problems are less common than
with liquid fuels. LPG has a lower energy density but higher octane rating than gasoline.
Consequently, LPG produces fewer miles per gallon but the octane value allows higher
compression ratios and higher power and fuel efŽ ciency. For the same compression ratio,
the amount of gaseous LPG air/fuel mixture that can be burned is about 5–10% less than
in gasoline engines. Overall, there usually is a small loss in engine power output. To
keep the range of LPG vehicles similar to gasoline vehicles, LPG vehicles will require
larger storage tank volume. For the same fuel volume, a LPG tank weighs more, but not
signiŽ cantly more, than a tank for gasoline.

LPG Safety and the Risk of Explosion or Fire


Over 4 million LPG vehicles are in operation in about 30 countries, such as Japan, the
Netherlands, Australia, Austria, and Italy, with proven safety records. The fuel tanks of
LPG vehicles are designed to withstand severe impact without rupture and can survive
vehicle Ž re. Overseas experience shows that LPG vehicles are at least as safe as diesel
and petrol vehicles.
A risk assessment consultant commissioned by us carried out a survey of previous
accident experience with gas-fuelled vehicles. The consultant found that there had been
very few accidents involving the fuel systems of gas vehicles. There were 4 reported
LPG vehicle accidents on the road. Details are at Annex 1. It should be noted that all
4 cases involved converted LPG vehicles, which are not allowed in Hong Kong. We
only allowed custom-made LPG vehicles produced by original vehicle manufacturers,
which are subject to very high safety and performance standards. Our risk consultant
has conŽ rmed that there have not been any accidents relating to the fuel system of
custom-made LPG vehicles.
The risk of explosion or Ž re associated with the use of mobile telephones in a LPG
vehicle is extremely low. First, LPG vehicle fuel systems are closed systems with safety
features to prevent accidental release of LPG. The risk of fuel leakage is less than that of
a petrol or diesel vehicle. Second, LPG will only burn when mixed with air in proportions
within the  ammable limits and when there is an ignition source.
606 A. Demirbaş

Working with higher-pressure fuel systems requires special tools and safety precau-
tions. Mechanics should receive special training and certiŽ cation. The training should
include the fundamentals of LPG combustion and storage, working with high pressure
conduit, connectors, regulators, and cylinders, safety codes and industry standards, cylin-
der inspections, conversion system calibration, and troubleshooting.

Fuel Properties of CNG


The composition of pipeline NG varies depending on the source and processing of the gas.
Typically, it is over 90% methane and small amounts of ethane and other hydrocarbons.
NG may also contain nitrogen, carbon dioxide, and trace amounts of water vapor.
NG at ambient temperatures and pressures is a gas. As is typical of gases, it has a
very low energy density compared to other fuels. On average, it takes 0.921 cubic meters
of NG to equal the same energy content as 1 l of gasoline. This makes use of NG as
a transportation fuel at ambient temperatures and pressures unfeasible. To use NG as a
transportation fuel it must either be compressed or liqueŽ ed to increase its volumetric
energy density.
The vapors of many liquid fuels such as gasoline and LPG are heavier than air. As
they evaporate, gasoline and LPG vapors tend to accumulate around the source and pose
an explosion hazard. NG requires a greater concentration in air and a higher temperature
to ignite than gasoline. In the event of a leak or accident, natural gas will ignite at a
temperature of 811 K and between 5% and 15% concentration in air. Gasoline will ignite
at only 533 K and 1.5% concentration in air.
Ventilation must be provided in CNG vehicle maintenance garages and vehicle stor-
age buildings through ceiling exhaust systems to prevent hazardous CNG accumulations.
In vehicle operation, as the pressure regulators reduce CNG pressure, the temperature
will drop, causing water vapor in the NG to condense. The condensed water will restrict
or block fuel  ow. CNG vehicle fuelling stations normally dehydrate the NG to prevent
water condensation.
Use of CNG as a transport sector fuel requires investment in a dramatically different
fuel supply system. Gas has to be taken from a gas distribution system, usually at a
pressure of 0.3 to 1 MPa, and compressed to 20 MPa into a vehicles’ CNG tanks.
Without intermediate storage at the CNG vehicle Ž lling station, a slow Ž ll system is used
that only has compressors. About 8 h are required for refueling the vehicles. For a more
rapid Ž ll, but usually no faster than 5 min, larger compressors and intermediate storage
are required.
Typically, to use CNG as a transportation fuel, NG is taken from a gas distribution
system at pressures ranging from 0.3 to 1 MPa, compressed at a fuelling station, and
stored in cylinders on vehicles at pressures of about 20 MPa. Currently, the international
NG vehicle industry has not set a standardized CNG pressure. At 20 MPa, the volumetric
energy density of CNG is about one-fourth that of gasoline. Thus, with all efŽ ciencies
being equal, a CNG vehicle requires 4 times the size of a gasoline tank for the same
driving range. Liquefying NG by cooling it to approximately ¡400 K increases its en-
ergy density. LiqueŽ ed natural gas (LNG) is typically stored at low pressures between
0.07 and 0.34 MPa to maintain its liquid state, but LNG is not available in most mar-
kets. Increasing the travel distance between refuelling increases the investment, weight
of the storage tank, and space given up for making it possible to use CNG. Natural
gas has an octane value of 130, which is considerably higher than gasoline, which usu-
ally ranges between 84 and 97. The higher octane of CNG generally gives very good
Fuel Properties of H2 , LPG, and CNG for Transportation 607

Table 4
World natural gas reserves by country

Reserves
Country (trillion cubic meter) Percent of world total

World 145.6 100.0


Top 20 countries 129.6 89.0
Russian Federation 48.1 33.0
Iran 23.0 15.8
Qatar 8.5 5.8
United Arab Emirates 6.0 4.1
Saudi Arabia 5.8 4.0
United States 4.7 3.3
Venezuela 4.0 2.8
Algeria 3.7 2.5
Nigeria 3.5 2.4
Iraq 3.1 2.1
Turkmenistan 2.9 2.0
Malaysia 2.3 1.6
Indonesia 2.0 1.4
Uzbekistan 1.9 1.3
Kazakhstan 1.8 1.3
Rest of world 23.0 16.5

Source: Worldwide Look at Reserves and Production, 1998.

engine performance characteristics. World natural gas reserves produced by countries


are given in Table 4.

Vehicle Operation with CNG


Despite the large difference in volumetric energy density between gasoline and CNG, the
impact of CNG energy density on engine performance is less dramatic. As a gas, it has
few cold-start problems. Its higher-octane value allows for higher engine compression
ratios than can be used with gasoline alone. Higher compression ratios allow for higher
power and fuel efŽ ciency. However, for the same compression ratio, the amount of natural
gas air/fuel mixture that can be burned in each piston stroke is 10–15% less than for
gasoline. Thus, there is a 10–15% loss of engine output power.
To use CNG safely, technicians and drivers need to know what the differences are
and how to work with them. Other subjects that must be understood are NG combustion
and storage, working with high pressure conduits, connectors, regulators, and cylinders,
safety codes and industry standards, and recommended CNG cylinder inspections. De-
tailed hands-on training for installation and maintenance technicians should normally be
provided by the conversion kit manufacturers.
In general, the use of NG results in cleaner and longer-lasting engines. Less carbon
builds up on spark plugs, engine oil, and in the combustion chamber. Natural gas has
higher ignition temperatures than gasoline, which increases the importance of maintaining
proper ignition system operation.
Table 5
Emissions of hydrogen and same model gasoline vehicles

Emissions, gkm¡1

Vehicle or engine Fuel Emission control NOX CO CH4 CO2 C 2 H4

Dodge D-SO Pickup Diesel oil PCV 1.19 0.44 0.26 8.66 0.12
Dodge D Pickup Gasoline CC, EGR 1.80 2.73 0.28 3.70 0.16
Musashi-2 Liquid H2 No CC 2.50 0.18 0.05 — 0.03

608
Ford 4 cyl Gasoline No CC 1.42 21.9 1.41 — 0.86
BMW 745i, 6 cyl Liquid H2 No CC 0.35 — — — —
BMW 745i, 6 cyl Liquid H2 No CC 0.27 — — — —
BMW 745i, 6 cyl Gasoline No CC 2.50 — — — —
MB 280 TE wagon H2 /gasoline No CC 0.52 1.87 2.17 — 0.95

PCV: positive crankcase ventilation.


CC: catalytic converter.
EGR: exhaust gas recirculation.
Source: ÇaÆglar and Özmen, 2000.
Fuel Properties of H2 , LPG, and CNG for Transportation 609

Environmental Impacts of Hydrogen, LPG, and CNG as Vehicle Fuels


Hydrogen has been suggested as a convenient, clean-burning fuel. Hydrogen made from
sustainable energy can ultimately replace fossil fuels, resolving the environmental, po-
litical, and resource concerns of their use. Hydrogen will also solve air pollution and
planet-warming problems in the future. Table 5 shows the emissions of hydrogen and
same model gasoline vehicles.
Changing to LPG use will reduce carbon monoxide (CO) emissions from these
vehicles by about half. Because of the technology, NOx emissions will probably decrease
by only 25% with LPG use instead of gasoline. CNG also has much lower environmental
impact than other hydrocarbon fuels when the process from production in the Ž elds to
Ž lling of the vehicle tanks is taken into account.
The toxic emissions with CNG, without exception, are lower than for any other
hydrocarbon fuel. This is a direct result of the fact that CNG is a single hydrocarbon,
90C% methane, whereas all of the other fuels are a mix of hydrocarbons. LPG is a
relatively simple mix of propane, butane, and pentane compared to CNG and the complex
mix that makes up the gasoline and diesel typically purchased at the service station.
Gasoline and diesel emit compounds into the air: methanol, formaldehyde, aldehydes,
acrolein, benzene, toluene, xylene, etc., some of which are not yet part of any established
emission standard but certainly are not beneŽ cial to peoples’ health.
Soot emission from hydrocarbon  ames is an important subject since it plays an
important role in relation to both heat transfer by radiation and air pollution (Shahad
and Mohammed, 2000). The use of CNG in internal combustion (IC) engines permits
operation with decreased advances decreases NOx without increasing soot formation or
speciŽ c fuel consumption.
The production, processing, transportation, and compression of NG to the CNG
fuel that is used by vehicles results in less environmental impact than the production,
transportation, and processing of crude oil and the transportation of gasoline or diesel
to the service stations. CO2 emission of NG is lower than both diesel fuel and gasoline,
which makes natural gas engines favorable also in terms of the greenhouse effect.

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