Alcohol:

• Methanol and ethanol were long considered good spark-ignition engine alternative fuels.

• A significant advantage of alcohol fuels is that when they are combusted in diesel engines,
they do not produce any soot or particulates and they can also be tuned to produce very
low levels of oxides of nitrogen.

• Emissions are less reactive in the atmosphere, producing smaller amounts of ozone, the
harmful component of smog. Compared to specially formulated petroleum fuels such as
California Phase 2 gasoline

• Methanol and ethanol have the disadvantage in that they produce formaldehyde and
acetaldehyde as combustion by-products in larger quantity than the toxic compounds
from the petroleum fuels that they replace
Methanol:
1930 – Grand prix
1960 – serious attention made base on emissions advantage
Low concentrations of methanol were found to be a good non – metallic substitute
Methanol requires incorporation of higher-order (C3 - C8) alcohols to obviate phase
separation deficiencies, and a 50/50 mixture with TBA was found to be more advantageous
than other organics
MTBE (Methyl tertiary Butyl Ether) – reacting methanol with Iso-butylene.
MTBE is an octane blending agent with more favorable characteristics than methanol to
produce blends with gasoline for use in existing gasoline vehicle models
Major disadvantages of methanol are:
• initial higher cost than that of gasoline;
• impact of reduced energy density on driving range or larger fuel tank;
• it burns with a flame that is not visible in direct sunlight;
• need for education of users and handlers on toxicity and safety
Production:
1995 – 6.5 billion liters and 21 ranked chemical & MTBE stood as 12th ranked and produced 10.0
billion liters
Large scale production was develop by Badische Anilin und Soda Fabrik (BASF) in Germany in
1924
Currently preferred process is steam reformation of natural gas (thermal efficiency of 56 – 62%)
Methanol can also be produced from coal and municipal waste.
• The American Methanol Institute (AMI) estimates that by the year 2010, methanol demand
for fuel cell vehicles alone may reach 882 million gallons per year
• At moderate pressures of 1 to 2 Mpa and high temperatures around 8500C, methane
reacts with steam on a nickel catalyst to produce syngas
CH4+H2O → CO + 3H2 (endothermic)
• On a second catalyst at 5 – 10 MPa, and 2500C it produce methanol
CO + 2H2 -> CH3OH
Most widely used catalyst is a mixture of copper, zinc oxide and alumina

New and more efficient ways to produce methanol from methane:

1. Methane oxidation with homogeneous catalysts in sulphuric acid media
2. Methane bromination followed by hydrolysis of the obtained bromomethane
3. Direct oxidation of methane with oxygen
4. Microbial of photochemical conversion of methane
Vehicle emission characteristics:
No soot
Poisonous
Invisible flame
Low NOx; contains no aromatic compounds therefore no benzene emissions
Methanol is less reactive in the atmosphere than hydrocarbons from diesel fuel make the
emission benefits of using methanol in diesel engines very positive.
Methanol exposure studies have shown that methanol does not cause harm in the quantities
that would accumulate in the body from exposure from refueling vapours or from unburned
methanol in vehicle exhaust
Evaporative emissions of methanol during transport, storage, dispensing, and use fall about
midway between gasoline and diesel fuel, but increase with use of gasoline/methanol
blends.
Emissions of M85 in spark-ignition light-duty vehicles have been shown to have significant
reductions in specific ozone-forming potential (about 50% grams ozone per gram emissions)
compared to conventional gasoline (40-45% reduction compared to California Phase 2
reformulated gasoline)
Tests of more recent model flexible fuel vehicles have shown that they can achieve very
similar emissions per mile as when using gasoline
The CO2 emissions of methanol vehicles are theoretically about 94% those of similar
petroleum-fueled vehicles, assuming they have the same fuel efficiency. When the entire
fuel cycle from resource through combustion is included, methanol has very similar green-
house gas emissions relative to gasoline.
Methanol contains no sulfur, so it does not contribute to atmospheric sulfur dioxide (SO2)
Vehicle performance impacts:
Methanol spark-ignition engines have the capability to be 15-20% more efficient than their
gasoline counterparts. This is achieved through lean-bum technology.
Ford built 630 dedicated methanol Escorts from 1981 to 1983. The engine in these vehicles
had 20% higher torque than the original gasoline versions. Acceleration from 0 to 60 mph was
15.8 seconds on M85 compared to 16.7 seconds on gasoline. Subsequent Crown Victorias had
an acceleration time of 12.2 seconds on M85 compared to 12.6 seconds on gasoline.
The fuel sensor of FFVs instantaneously (under 50 milliseconds) determines the concentration
of methanol in the fuel
FFVs do leave room for improvement as General Motors demonstrated by optimizing a 3. 1L
Lumina to dedicated M85 operation. The engine compression ratio was increased from 8.9
(used in the FFV version) to 11.0. This was obtained by use of a smaller piston bowl, reduced
crevice volume, etc. A close coupled 80-cu.-in. palladium catalyst was added to the 170-cu.-in.
palladium/rhodium one. Not only was performance increased, but fuel economy was
increased while emissions were decreased. This vehicle was even then very close to meeting
the California ULEV emissions standards.
 FFV: Flexible Fuel Vehicle
TLEV: Transitional Low Emission Vehicle –
least-stringent california vehicle emission
LEV: Low Emission Vehicle – second
most-stringent california vehicle emission
ULEV: Ultra Low Emission Vehicle – most-
stringent california vehicle emission
NMOG: Non-Methane Organic Gases
HCOH: Hydroxy Methylene
(Formaldehyde)
OMHCE: Organic Matter Hydrocarbon
Equivalent – A weighted measure of hydrocarbon
emissions based on the reactivity of all the
components

Fig: Table showing difference of FFV and

dedicated M85 of 3.1 L Lumina (GM)
Methanol applications:
• A laboratory solvent for high performance liquid chromatography (HPLC) and ultraviolet (UV)
spectroscopy
• A fuel for the direct methanol fuel cell (DMFC)
• An antifreeze solution in pipes
• A solvent for chemical applications
• A waste water treatment chemical
• A windshield washer fluid
• A source for producing dimethyl ether (DME) and formaldehyde
• A multipurpose fuel for Internal combustion (IC) Engines
• As a gas turbine fuel for aviation and power generation
 Fuel specifications and Properties

• Properties of a fuel define its physical and chemical characteristics

• Fuel specifications represent an attempt to mold and limit fuel properties to facilitate
use in vehicles and limit the hazards presented in storing and handling fuels
• Fuel specifications also serve a very valuable service as a means of standardizing fuel
properties, which facilitates trade and commerce of that fuel.
• Fuel distribution system is based on the concept of fuel fungibility.. Tha ability to trade
fuels within a wide region without fear of problems due to variations in fuel properties.
• Fuel specifications include tests that evaluate the performance characteristics of a fuel.

Vapour Pressure: Equilibrium pressure exerted by vapors over a liquid at a given temperature.
The Reid vapor pressure (RVP) is typically used to describe the vapor pressure of petroleum
fuels without oxygenates at 100°F (ASTM Test Method D 323, Test Method for Vapor Pressure
of Petroleum Products). The term "true vapor pressure" is often used to distinguish between
vapor pressure and Reid vapor pressure. The Reid vapor pressure test involves saturating the
fuel with water before testing and cannot be used for gasoline-alcohol blends or neat alcohol
fuels; a new procedure has been developed which does not use water and is called Dry Vapor
Pressure Equivalent, or DVPE (see ASTM D 4814-95c under Additional Information section)
Methanol:

o Colourless, light weight with faint odour liquid

o 30 – 90 g more than a liter of typical gasoline

o Boils at one temperature (650 C)

o Methanol is much less prone to produce flammable vapor at ambient temparature.

o Methanol's low viscosity has been identified as a reason methanol compression-ignition

engines start much more quickly than compression-ignition engines using diesel fuel

o Completely soluble in water. Less than 10% water would not significantly affect the
combustion characteristics of methanol, though it would significantly affect the profitability
of selling the fuel and possibly the long-term durability of the engines using it.

o Static electric charge induced from fuel movement into and out of fuel tanks will dissipate
much more quickly.
o Methanol has a latent heat of vaporization nearly 3.4 times that of gasoline on a mass basis.
Since it takes approximately twice as much methanol as gasoline, the overall effect is nearly
seven times as high. This is an advantage to the power output of spark-ignition engines
because the latent heat cools the intake air, making it more dense. It also decreases the
propensity for autoignition by cooling combustion temperatures, which also results in lower
emissions of oxides of nitrogen, one of the major contributors to ozone formation.
Methanol's high latent heat of vaporization is a safety concern in cold weather since skin
contact can quickly cause frostbite.
o The flash point of Methanol is 11°C (52°F) compared to gasoline at -43°C (-45 0F). A gasoline
engines modified to use methanol found that starting would occur only at temperatures
above 70C.

o The autoignition temperature of methanol is nearly twice that of gasoline

o Methanol achieves flammability much later and stays in the flammable.

o The flame spread rate of methanol is about two-thirds that of gasoline.

o A very serious safety deficiency of methanol is that it bums without a visible flame in daylight
which makes fire detection and fire fighting difficult. The invisible flame is an indication of
the soot-free combustion properties of methanol.

o A moderate safety advantage of methanol flames is that they have low radiant heat transfer,
meaning that surfaces close to a methanol flame will not get as hot as compared to a
o The average octane of methanol is at least 5 numbers higher than the highest octane
unleaded premium gasoline available, and 12 numbers more than the typical unleaded
regular grade of gasoline.
 Materials Compatibility
The primary areas of concern for materials compatibility include corrosion of metals and
impacts on the elastomers used in the engine, primarily in the fuel system.

The elastomer impacts include swelling, shrinking, hardening, cracking, and other changes that
lead to failure of the part and cause for the evaporative emissions.

The most common job for elastomers in fuel systems is to prevent leaks from fittings and
joints

A growing concern for materials compatibility is increasing amount of plastics used in vehicle
fuel systems.
 Materials Compatibility for Methanols

Most aggressive , affecting both metals and elastomers

Magnesium and alluminium materials are corroded by Methanol. This corrosion

(particularly alluminum hydroxide) will plug filters and cause operating problems with
fuel injectors and increased engine wear.

General Motors has determined that aluminium hydroxide concentrations of 0.1 mg/L are
the limit to ensure vehicle fuel filter life 40,000 km.

Ordinary carbon steel is surprisingly one of the metals least affected by methanol that is
“dry” (does not contain significant amounts of dissolved water) and free from foreign
matter and impurities.

Other impurities that cause methanol to become more corrosive include sodium formate
(HCOONa), organic peroxides, sulfur compounds, and reactive metals.

Stainless Steel also least affected by methanol.

Brass, bronze, and die cast zinc have been found to be corroded more quickly by
methanol than by gasoline. Copper is to be avoided, not only because it is likely to be
corroded by methanol, but because it is not suitable for hydrocarbon fuels.
Several corrosion inhibitors such as polyamide, polyamine, dithiocarbamate,
thiophosphate ester, organic acid, sulfide, and selenide types have all been tried in
methanol without significant success.

One area where coatings have proven effective is in prevention of anodic dissociation of
fuel pumps immersed in methanol. Polyolefin coatings have been found to be effective in
preventing such metal removal

Nickel as metallic coating found to be reliable to reduce corrosion and can be applied to
steel and aluminium.

Fiberglass not designed for methanol will quickly soften and delaminate storage tanks.
Ford has reported that onboard fuel lines made of poly phenylene sulfide resin give good
performance.

Cross-linked polyethyle has been found to be compatible hose for methanol fuel.

High-flourine-content elastomers and teflon have proved to be compatible with methanol.

Buna-N, Viton, rubber, nitrile, acrylate, polyurethane, and most plastics are attacked by
methanol. Methanol may also attack cork and methyl methacrylate.
 Storage and Dispensing
The favored method of storage for both
gasoline and diesel fuel has been under
ground tanks made of steel or fiber glass.

Service stations with multiple dispensers

uses submerged pumps.

Underground Storage Tanks (USTs):

• The fuel stays at a relatively constant

temperature
• Refilling can be done using gravity feed
rather than using a pump

Four requirements for new UST regulations:

1. The owner or operator must certify that

the UST is installed properly.
2. The UST must be protected from
corrosion
3. The UST must be equipped with devices that
prevent spills and overfills.
4. The UST must have a leak detection method
that provides monitoring for leaks at least
every 30 days.
Leak detection methods used with UST:
❑ Tank tightness testing (twice yearly) and
inventory control
❑ Automatic monitoring of product level and
inventory control
❑ Monitoring of vapours in the soil
❑ Monitoring for liquids in the ground water.
❑ Monitoring an interception barrier.
❑ Interstitial monitoring within secondary
containment.
❑ Other methods as approved by EPA

USTs containing hazardous materials must have

secondary containment.
 Storage and dispensing of Methanol

Methanol is a highly polar liquid that is completely miscible with water.

Stainless steel is the best material for methanol tanks, pipes, and components.
Anodised aluminium has shown better resistance than plain aluminium, but it will
eventually corrode like aluminium.
The elastomer least affected by methanol is teflon, though elastomers with high flourine
content have been shown to be acceptable.
Tanks:
Underground piping must be double walled.
Methanol tanks can be made from stainless steel, carbon steel, or fibre glass.
The epoxies made for gasoline are not compatible with methanol and will come off the
walls of the tank within a short time, causing major problems with pumps and filters.
Methanol and Ethanol must be stored in USTs having secondary containment.
Secondary containment includes:
❑ Double-wall tanks
❑ Placing the tank in a concrete vault
❑ Lining the excavation area surrounding the tank with natural or synthetic liners that
can not penetrated by chemical

Conservation vents are recommonded for methanol. These are usually configured to
venting only when the pressure in the tank exceeds 7 – 21 kPa, and when vacuum in the
tank exceeds 5 – 10 cm. of water.
Piping:

Piping for methanol can be stainless, carbon steel, or fiberglass. When using carbon steel, it is
important to use only black steel and not galvanised steel.

Because methanol is classed as a hazardous chemical by the EPA, all piping placed
underground must have secondary containment. Piping above-ground need not have
secondary containment.

For threaded pipe connections, the preferred pipe dope is teflon paste or teflon tape. Almost
all pipe dope developed for use with gasoline will be dissolved by methanol, creating leaks.

Dispensers:
Dispensers for gasoline and diesel fuel typically use steel, cast iron, aluminium, brass,
bronze, and sometimes stainless steel components. Of these, only the steel, cast iron, and
stainless components are compatible with methanol. The other parts will need to be
nickel-plated or substitutes made from a compatible metal.

Gasboy, Tokheim, and Wayne – Dresser have produced methanol compatible versions of
their gasoline dispensers

The most durable methanol dispenser filters to date have used nylon filter elements and
methanol-compatible glue. It is recommended that the filter elements used in methanol
dispensers be 3 µm mean diameter, instead of the 10 µm filters common for gasoline.
Goodyear has developed methanol-compatible dispensing hose which is easily recognised
since it is green or blue in colour. It is coaxial, making it compatible with vapor recovery
systems. Though this hose is compatible, ford motor Co. has found it to release plasticizers
when methanol is first put through it, which can obstruct vehicle fuel filters. Ford’s
recommendation is to soak the hose in methanol for 24 hours before putting it into use.

Emco-Wheaton makes a dispensing nozzle compatible with methanol and configured for
vapor recovery systems.
Miscellaneous Components:

Breakaway fittings are available in stainless steel which is compatible with methanol.

Leak Detection Systems:

Active leak detection systems that rely on thermal conductivity and electrical resistivity
sensors will not work with methanol because its properties are so different from gasoline.
Another type of active leak detection system that will work with methanol or any other
type of fuel relies on changes in impedance in a sensor wire as it becomes wetted with the
fuel.
Fire Suppression Systems:

Most of these systems are dry chemical using infrared detectors and work as effectively on
methanol vehicle fires as gasoline vehicle fires.

Lightning Protection:

Generic building codes are available for lightning protection(NFPA 180) which should be
followed and supplemented by local building code requirements.
 Refueling Facility Installation and Garage Facility Modifications

The most pertinent NFPA codes include NFPA 30 – Flammable and Combustible liquids
code, and NFPA 30A – Automotive and Marine Service Station Code.

The objective of this chapter is to present information that could be useful in educating
local officials in the building code and safety issues involving alternative fuels and to
provide what information is available for each.

All vehicle fuels raise safety concerns. These are mainly associated with the physiological
properties of the fuel, e.g., toxicity, and with its flammable properties.

Personnel should be informed about the properties of the alternative fuel, and safe
practices for operating, refueling, and maintaining alternative fuel vehicles.

It is imperative that those wishing to install alternative fuel refueling systems, and store
and maintain alternative fuel vehicles indoor, do a comprehensive analysis of their
situation, and research the pertinent codes in detail before applying for building permits
and initiating construction drawings.
 Refueling Facility Installation and Garage Facility Modifications for Alcohols

Building codes become law only when they are adopted by the local authority having
jurisdiction, which is usually the local fire marshall

1. The National Fire Protection Agency (NFPA)

2. The International Fire Code Institute (IFCI)
3. The Building Officials and Code Administration (BOCA)
4. Southern Building Code Congress International (SBCCI)
NFPA 30 – Flammable and Combustible liquid code
NFPA 30A – Automotive and Marine service station code

Other than propane and CNG refueling systems, it is unlikely that local jurisdictions will have
building codes specific to alternate fuels.

Alcohols are flammable liquids which are covered in NFPA 30, Class IB as a
Flammable and Combustible Liquids Code.
Gasoline is included under NFPA 30 as a class IA as a Flammable liquid, while diesel fuel is
included as a combustible liquid
Location of Storage Tanks:
Where storage tanks can be placed depends on: whether they are above ground or
underground; the nearest building, property line, or public way; the type of organization that
uses the tank and how it is used; and for above – ground tanks, whether they are fire resistant
or not
1. Above-Ground Tanks:
According to NFPA 30A, above-ground tanks are limited to 12000 gal. capacity each, and
multiple tanks manifolded together cannot exceed 40,000 gal. Above-ground tanks
Must be placed at least 15 m from the nearest important building or public way, and at
least 30 m from any property line. These distances can be reduced by half if the above-
ground tank is fire resistant.
2. Underground Tanks:
According to NFPA 30, underground tanks containing alcohol fuels must be placed at least
0.3 m from the wall of any basement or pit. They also must be atleast 0.9 m from any
property line. EPA underground storage tank regulations specify that USTs and their lines
must have secondary containment.
Location and Installation of Fuel Dispensers:
NFPA 30A does not specify limits on the location of fuel dispensers except that they must be at
least 6m from any fixed source of ignition. Dispensers should be solidly mounted on a
refueling island or some similar equivalent means. Protection should be provided in the form
of bollards or guardrail to prevent errant vehicles from colliding with the dispenser. For above-
ground tanks, dispensers can be mounted directly on the tanks.
Dispensing hoses are limited to 5.5 m and must have a breakaway device in the event a vehicle
drives off without removing the refueling nozzle.
Vehicle Storage and Maintenance Facilities:
Alcohol vapors from released fuel are heavier than air similar to gasoline vapor, and represent
similar fire safety hazards.
The ventilation rates recommended for conventional fuels should be sufficient for alcohol
fuels.
 Fire Protection:

Dry chemical fire suppression systems are the most appropriate for use at vehicle fuel storage
and dispensing systems. The discharge nozzles should be placed both overhead and at curb
level so that the entire area prescribed by the radius of the dispensing hose will be covered.
Testing of the nozzle placement should be done by using a “puff test” in which the dry
chemical is discharged on purpose to verify coverage. The puff test is triggered by creating a
small controlled fire of the fuel used which also tests the fire detection sensors, usually
ultraviolet and infrared.

Check valve is located between the storage tank and dispenser

 Pressurizing and moving fuel:
1. Self contained: pumping unit located inside a dispenser
2. Remote pump : Mostly used in now a days

1. Self – contained pump: Pressure after the pump is 18

to 25 PSI
• After air separator flow to the automatic check valve

2. Remote pump: Pump is located at or in the storage

tank. The basic elements are:
• The air eliminator and system check valve are
located inside the discharge head
• Even when one of the dispenser is on all the pipe
lines connected to the pump are pressurized to 24
to 28 PSI

Fig.: Remote system Emergency shut

off valve

Fig.: Remote dispenser control valve

the discharge nozzle performs three basic control functions

• controls fuel delivery,

• prevents vehicle tank over-fill (when the nozzle is so-equipped), and

• prevents the discharge hose from draining after completion of a delivery.