report no.

3/08

Guidelines for
blending and
handling motor
gasoline containing
up to 10% v/v ethanol
 report no. 3/08

Guidelines for
blending and
handling motor
gasoline containing
up to 10% v/v ethanol
Prepared for the CONCAWE Fuels Quality and Emissions Management Group by
its Special Task Force, FE/STF-24:

B. Engelen (Chair)
L. Baldini
J. Baro
J. Delgado Diestre
N.G. Elliott
E.B.M. Jansen
P-M. Martinez Sánchez
S. Mikkonen
M. Mortier
P. Scorletti
R. Terschek
J. Woldendorp

K.D. Rose (Technical Coordinator)

N.D. Thompson (Technical Coordinator)

Reproduction permitted with due acknowledgement

© CONCAWE
Brussels
April 2008

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 report no. 3/08

ABSTRACT

This report provides guidance on handling and blending ethanol at up to 10% v/v
concentrations in motor gasoline. The major challenges associated with ethanol-
containing gasolines are discussed as they relate to the conformity of the finished
fuel to typical specifications, especially those in the European unleaded motor
gasoline specification (EN228). This report focuses on the production, distribution,
and supply of motor gasoline containing up to 10% v/v ethanol and does not
address issues related to higher ethanol blends, specifically E85 fuels (up to 85%
v/v ethanol in gasoline).

For the purposes of this report, the terms motor gasoline and unleaded petrol (as
defined in European Standard EN228) are considered to be synonymous.

KEYWORDS

Ethanol, motor gasoline, unleaded petrol.

INTERNET

This report is available as an Adobe pdf file on the CONCAWE website

(www.concawe.org).

NOTE
Considerable efforts have been made to assure the accuracy and reliability of the information
contained in this publication. However, neither CONCAWE nor any company participating in
CONCAWE can accept liability for any loss, damage or injury whatsoever resulting from the use
of this information.

This report does not necessarily represent the views of any company participating in CONCAWE.

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 report no. 3/08

CONTENTS Page

SUMMARY IV

1. INTRODUCTION 1
1.1. MAJOR CHALLENGES 1
1.2. OTHER CHALLENGES 1

2. CHALLENGES AND GUIDELINES 2

2.1. VAPOUR PRESSURE 2
2.2. DISTILLATION 3
2.3. OCTANE 4
2.4. HYDROCARBON BLENDSTOCK QUALITY 5
2.5. HYDROPHILIC NATURE 5
2.6. REMOVAL OF DIRT 7
2.7. MATERIAL COMPATIBILITY, CORROSION AND
PERMEABILITY 8
2.8. SULPHATE ISSUES 11
2.9. DENATURANTS ISSUES 11
2.10. TRANSPORT OF ETHANOL BLENDS 11
2.10.1. Transport via Multi-Product Pipelines 11
2.10.2. Transport by Road and Rail 12
2.10.3. Transport by Barge 12
2.11. SAFETY & FIRE FIGHTING MEASURES 12
2.11.1. Safe Handling 12
2.11.2. Surface Spills and Leaks 12
2.11.3. Fire Protection and Fire-Fighting Agents for Fires Involving
Ethanol/Gasoline Blends 12
2.11.4. Storage 13
2.11.5. Sources of Ignition 13
2.11.6. Drain or Waste Water Handling 14
2.12. ADDITIVE EFFECTS 14

3. BLENDING GUIDELINES 15
3.1. REFINERY BLENDING 15
3.2. TERMINAL BLENDING 15

4. GLOSSARY 16

5. ACKNOWLEDGMENTS 17

6. REFERENCES 18

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 report no. 3/08

SUMMARY

The production of motor gasolines containing ethanol will increase in Europe as a

consequence of the EU Biofuels Directive 2003/30/EC and the subsequent EU Fuel
Quality and Renewable Energy Directives that are expected to be adopted in 2008.
The increased use of ethanol introduces new challenges to refinery and vehicle fuel
systems and to an increased need for good housekeeping practices throughout the
gasoline supply and distribution system. This report provides guidelines for the
production, blending, distribution, and supply of motor gasolines containing up to
10% v/v ethanol.

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 report no. 3/08

1. INTRODUCTION

There is relatively little experience with biofuels in Europe although the production of
motor gasoline1 containing biomass-derived products, especially ethanol, is
increasing as a result of the EU Bio Fuels Directive 2003/30/EC and the subsequent
EU Fuel Quality and Renewable Energy Directives that are expected to be adopted
in 2008. The increased use of ethanol introduces new challenges to refinery and
vehicle fuel systems and an increased need for good housekeeping practices
throughout the motor gasoline supply and distribution system.

Although new vehicle technologies (Flexible Fuel Vehicles) have been developed
that can use fuel blends containing up to 85% v/v ethanol (also known as Ethanol
(E85)), this document only addresses the challenges of motor gasoline blends
containing up to 10% v/v ethanol.

Several general references on ethanol and ethanol/gasoline blends are also

included in the bibliography section. [1,2,3,4,5,6]

1.1. MAJOR CHALLENGES

The chemistry of ethanol is very different from that of hydrocarbon fuels. As a result,
blending ethanol into hydrocarbon fuels introduces some specific challenges that
must be carefully addressed in the production, blending, distribution, and supply of
motor gasolines, including:
• Effect of ethanol on vapour pressure, octane rating, distillation, and related
properties,
• Quality of the hydrocarbon blendstock for ethanol blending to ensure fit-for-
purpose motor gasoline performance, and
• Tendency of ethanol to increase the dissolved water content of motor gasoline.

1.2. OTHER CHALLENGES

Other challenges can also be expected as the use of ethanol increases. In general,
these challenges are managed through proper specifications, procedures, and good
housekeeping practices, and include:
• Removal of dirt, rust, and other solid contaminants,
• Compatibility of motor gasoline containing ethanol with materials commonly
used in refinery, distribution, and fuel supply systems, especially the
permeability and corrosion of these materials,
• Sulphate issues - product handling and injector plugging in vehicle fuel systems,
• Denaturants issues,
• Transport of gasolines via multi-product pipelines,
• Safety and fire-fighting measures,
• Effects of corrosion inhibitor additives,
• Guidance on ethanol blending at refineries and terminals.

1
For the purposes of this report, the terms motor gasoline and unleaded petrol (as defined by European
Standard EN228) are considered to be synonymous.

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 report no. 3/08

2. CHALLENGES AND GUIDELINES

2.1. VAPOUR PRESSURE

Although ethanol has a lower molecular mass than most of the hydrocarbons used
in motor gasoline, ethanol is a liquid rather than a gas at ambient temperatures and
pressures due to strong intermolecular hydrogen bonding interactions between
ethanol molecules. These interactions are either very weak or absent in
hydrocarbon mixtures. As a consequence, pure ethanol has a much lower vapour
pressure (15-20kPa) than motor gasoline.

However, when ethanol is dissolved into a predominantly hydrocarbon mixture such

as motor gasoline, these same intermolecular interactions increase the volatility of
the hydrocarbon-ethanol blend, most significantly at low concentrations of ethanol.
For example, the maximum increase in vapour pressure occurs at an ethanol
concentration of only about 1-5% v/v ethanol in a hydrocarbon blend. This positive
deviation from ideal mixture behaviour (Raoult’s Law) occurs because the
intermolecular interactions between ethanol and hydrocarbon molecules are less
than they are in the two pure liquids making it easier for molecules to volatilize from
the ethanol-hydrocarbon mixture.

As shown in Figure 1, addition of only about 2% v/v of ethanol into unleaded

gasoline can increase the vapour pressure of the mixture by 6-8 kPa potentially
leading to non-compliance with the requirements of European Standard EN228,
EU’s quality standard for motor gasoline. The vapour pressure increase with low
concentrations of ethanol is also observed to be larger when the vapour pressure of
the base gasoline is reduced.

Figure 1 Vapour Pressure of Mixtures of Unleaded Gasoline 95 (ULG95) and Ethanol

P (kPa) P (kPa)
80 70

70
60
60
50 50
0 5 10 15 20 25 30
40 Ethanol (% v/v)

30 fuel 1
fuel 2
20
10
0 20 40 60 80 100
Ethanol (% v/v) Source: CONCAWE
Source: Kuwait Petroleum International

Because of this effect, mixing hydrocarbon-only and ethanol-containing gasolines in

the fuel distribution and supply system, for example, can also result in a vapour
pressure increase that can cause the mixture to exceed vapour pressure
specification limits. For this reason, it is recommended that hydrocarbon-only motor

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gasoline is not re-introduced into a section of the fuel distribution system once
ethanol-containing gasoline has been introduced. Mixing of hydrocarbon-only and
ethanol-containing gasoline cannot be avoided in the vehicle’s tank, however, and
cannot be controlled by fuel suppliers’ procedures.

Figure 2 shows the change in Dry Vapour Pressure Equivalent (DVPE) of three
different ethanol-free gasolines when blended with a 5% v/v ethanol-containing
gasoline (also containing 1250 ppm of water). The final ethanol content of these
blends ranged from 0% to 5% v/v ethanol.

Figure 2 Dry Vapour Pressure Equivalent (DVPE) of Blends of Ethanol-free and

Ethanol-containing Motor Gasolines

64 64
63 63
62 62
DVPE (kPa)

61 61
60 60
Ethanol-free Fuels:
59 ‹A – Super Unleaded Petrol (SUP) 59
▲B – SUP containing 5% v/v MTBE
58 z C – SUP containing 5% v/v ETBE
58
57 57
56 56
100 90 80 70 60 50 40 30 20 10 0
% EtOH-free Fuel
Ethanol content (% v/v) after blending each Ethanol-free Fuel with Ethanol-containing Fuel:
0% 1% 2% 3% 4% 5%

Each Ethanol-free Fuel was blended with an Ethanol-containing Fuel (5% v/v
ethanol & 1250ppm water) before the DVPE of the final blend was measured

Source: DGMK [7]

At the first introduction of ethanol-containing gasolines into the fuel distribution

system, the vapour pressure for delivered fuel should be targeted with an extra
margin in vapour pressure in order to ensure that marketed fuels do not exceed
vapour pressure specifications at the service station. From experience, this is more
easily managed in the winter time. Following first introduction, seasonal transitions
during the spring and autumn periods must also be carefully managed.

2.2. DISTILLATION

In addition to its impact on vapour pressure, ethanol also changes the distillation
characteristics of the gasoline/ethanol mixture and the evaporated fraction at 70°C
(E70) is changed most significantly.

As shown in Figure 3, E70 increases by about 8% v/v when 5% v/v ethanol is

blended into base gasoline. An 18% v/v increase in E70 is observed when 10% v/v

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ethanol is blended into base gasoline. These changes are significant and can be
compared to the 28% v/v overall range of E70 that is defined in the EN228
specification for all volatility grades (for example, for Class A motor gasolines, the
allowed E70 range is 20 to 48% v/v, or 28% v/v, in the EN228 specification).

Figure 3 Change in the Percent Evaporated versus Temperature for Motor Gasolines
as a Function of the Added Ethanol Content

225
T (°C)
200
Ethanol %%%
vol.
175
0
150 1
5
125 10 E 70 class A/B

100 E 70 class C/F

75 E 100 class A/F

50

25
0 10 20 30 40 50 60 70 80 90 100
Evaporated (% vol) Source: Kuwait Petroleum
Source:International
CONCAWE

2.3. OCTANE

Equation 1 can be used to estimate the RON and MON of gasoline blended with
ethanol based on the ethanol content and properties of the base and blended fuels.

Ca C
Equation 1: ON g +a = ⋅ I a + (1 − a ) ⋅ ON g
100 100
where:

ONg+a is the octane number (RON or MON) of the gasoline-ethanol mixture,

ONg is the octane number (RON or MON) of the base gasoline,
Ca is the ethanol content (% v/v), and Ia is the octane blending index of ethanol.
(Ca and Ia are dependent variables).
The octane blending index of ethanol, Ia, depends on the properties of the base
motor gasoline, and can only be determined by preparing and measuring the
properties of trial blends.

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 report no. 3/08

Since the octane of ethanol is higher than that of gasoline, there will normally be a
boost in motor gasoline octane after blending with ethanol and typical values are
shown in the table:

Typical Boost in Octane Number After Ethanol Addition

RON MON
2% v/v ethanol 0.5 0.3
5% v/v ethanol 1.3 0.8

Notes:
(1) The octane number boost depends upon the composition of the base gasoline, particularly its
aromatics content.
(2) The octane blending index for ethanol increases as the octane number of the base gasoline
decreases.

2.4. HYDROCARBON BLENDSTOCK QUALITY

For refiners producing motor gasolines containing ethanol, an important

consideration is the production and properties of the hydrocarbon blendstock for
ethanol blending, often called a Blendstock for Oxygenate Blending (BOB). This
hydrocarbon blendstock must be produced with properties that are appropriately
adjusted in order to take into account any changes that will occur after the ethanol
has been added, either at the refinery or terminal (see Section 3).

The current EN228 petrol specification permits the addition of up to 5% v/v ethanol
and this specification and its corresponding national annexes apply to motor
gasoline sampled at the service station nozzle. For this reason, the following
parameters should be considered when manufacturing the hydrocarbon blendstock
intended for blending with ethanol:

• Percentage volume of ethanol to be blended into the hydrocarbon blendstock

• The properties of the final motor gasoline that will be impacted by adding
ethanol to the hydrocarbon blendstock, such as:
− Vapour pressure (see Section 2.1)
− Distillation characteristics (see Section 2.2)
− Octane number (see Section 2.3)
− Oxygen content
• Seasonal adjustments and other local volatility requirements.

2.5. HYDROPHILIC NATURE

Due to the presence of the hydroxyl (-OH) group, ethanol exhibits strong hydrogen
bonding interactions, very similar to those found in liquid water. This effect means
that ethanol is hydrophilic in nature and has a strong affinity for water.

As a consequence, ethanol has a tendency to absorb water that may be present in

distribution, storage, and vehicle fuel systems even when the ethanol is only present
at low concentrations in gasoline. This tendency means that extra precautions are
required especially when ethanol is first introduced into the supply and distribution

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 report no. 3/08

system and good housekeeping practices are needed thereafter following its first
introduction.

The turbidity point, or haziness, is a good measure of the onset of phase separation
as a function of the water content of the fuel blend. If excess water is present,
ethanol can increase the concentration of dissolved water in gasoline before phase
separation (turbidity) is observed.

As shown in Figure 4, at the same turbidity point, the dissolved water content of
gasoline increases as the ethanol concentration in the blend increases. At the same
ethanol content, the addition of a co-solvent, tertiary-(n-butyl) alcohol (TBA) in this
example, increases the dissolved water content of the gasoline even further before
the onset of haziness or turbidity.

For example, at 1% v/v ethanol and at -10°C, gasoline becomes hazy at a water
concentration of 200 mg/kg. At an ethanol content of 5% v/v and at the same
temperature, haziness occurs at a much higher dissolved water concentration of
about 2000 mg/kg. In other words, ethanol is an effective co-solvent for dissolving
water in hydrocarbon fuels.

Figure 4 Turbidity Point (in deg C) of Motor Gasolines Containing Ethanol

as a Function of the Water Content (in mg/kg)

30

20
Turbidity Point (deg C)

10

-10

-20

-30

-40
0 500 1000 1500 2000 2500 3000 3500
Water Content (mg/kg)

1% EtOH 3% EtOH 5% EtOH

1% EtOH/0.5% TBA 3% EtOH/0.5% TBA 5% EtOH/0.5% TBA
1% EtOH/1% TBA 3% EtOH/1% TBA 5% EtOH/1% TBA

Fuels tested in this study included:

• Regular unleaded motor gasoline with vapour pressure ~90 kPa and 25% aromatics
• Regular unleaded motor gasoline with vapour pressure ~90 kPa and 35% aromatics
• Super unleaded motor gasoline with vapour pressure ~60kPa and 25% aromatics
• Super unleaded motor gasoline with vapour pressure ~60 kPa and 35% aromatics
All fuels contained no ETBE or MTBE and the turbidity points were tested twice at each
condition. (Source: DGMK [7])

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If phase separation does occur, the gasoline in the upper phase will usually contain
less ethanol than does the lower phase and may be out of specification for other key
properties, such as octane, vapour pressure, and distillation properties.

The lower phase will usually contain ethanol (~70%), water (~20%), and
hydrocarbons (~10%). Any water soluble denaturants, such as methanol, may also
be more soluble in the water phase than in the gasoline phase. Obviously, vehicles
will have difficulty running on a phase-separated mixture of this kind.

If it is found that phase separation has occurred, all dispensers should be

immediately deactivated and it is imperative that water bottoms are removed from
the storage tank. The remaining hydrocarbon mixture should be tested to ensure
that it is still in specification and, if not, appropriate action should be taken to remedy
the situation. Since the water bottoms will contain some level of ethanol and
hydrocarbons, this mixture may be flammable and appropriate precautions should
be taken during handling and disposal, consistent with local safety and
environmental regulations.

Extra precautions are also needed to avoid water entering tanks. Tank cleaning,
regular water checks and, if necessary, tank draining are advisable. It is also
recommended that tanks are adequately dried before their first use. Terminal
storage tanks should have fixed roofs with a floating internal cover. In-tank blending
is not recommended unless water entry is properly controlled. When checking
gasoline storage tanks for water, ethanol-compatible water paste should be used in
order to guarantee proper indication.

Because existing automatic water detection systems are disabled in the presence of
ethanol-containing gasoline, the use of ethanol in pipeline systems is not
recommended without taking special precautions (see 2.10.1). Ethanol-containing
gasoline can also interfere with the protection offered by commonly used corrosion
inhibitors in pipeline systems.

2.6. REMOVAL OF DIRT

Ethanol-gasoline blends may loosen sediment and sludge from storage tanks and
filling lines due to the solvency of the blend. For this reason, tanks should be clean
and free of water and sediment before they are used for ethanol-containing
gasolines.

The first load of ethanol-containing gasoline should fill the tank to at least 80%
capacity. If this is not accomplished with the initial load, a second load should be
brought in as soon as possible after the first load. This allows the solvency of the
ethanol-gasoline blend to loosen any sediment and varnish type deposits from the
sides and upper portions of the tank.

It is also recommended that storage tanks are kept as full as possible during the first
seven to ten days to accelerate this process and to run a few litres of fuel product
through each dispenser to flush the system. As soon as the dispensed fuel product
is clear and bright, the tank can be placed back in service. Dispenser filters should
also be changed if needed and 10µm (nominal) ethanol-compatible dispenser filters
are recommended for this purpose.

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2.7. MATERIAL COMPATIBILITY, CORROSION AND PERMEABILITY

Only the fuel distribution system is considered in this section, and not the fuel
system components commonly used on vehicles.

With respect to the compatibility with materials typically used in fuel supply and
distribution systems, ethanol is different from fuel hydrocarbons in three important
ways:
• The presence of the polar hydroxyl (-OH) group,
• The relative size of the ethanol molecule, and
• The higher conductivity of ethanol (and of ethanol/gasoline blends).

Because of these differences, various components in the fuel distribution system

may be less compatible with ethanol/gasoline blends than they are with
hydrocarbon-only fuels.

1. Many fuel system elastomers that have excellent compatibility with

hydrocarbon-only fuels are themselves characterized by polar constituents.
These constituents contribute to the stability of the elastomer through
hydrogen-bonding and other interactions. These interactions may be
vulnerable to substitution by the hydroxyl group of the ethanol. For this
reason, some elastomers can lose their structural integrity over time due to
the loss of stabilizing hydrogen bonding interactions when the elastomer is
exposed to ethanol/gasoline blends. Ethanol can also extract plasticizers in
the elastomers, reducing the flexibility and toughness of the elastomer
products. Fuel system components such as seals, gaskets and piping that are
made from polymers and elastomers must be designed to retain their
structural integrity, strength and flexibility after extended exposure to
ethanol/gasoline blends.

2. Because ethanol is a smaller and more polar molecule than MTBE, ETBE,
and other oxygenates, there is a lower energetic barrier for ethanol diffusing
into and through elastomeric materials. Over time, ethanol can accumulate in
these materials, causing them to swell and soften, leading to an overall
weakening of the elastomeric structure.

3. In comparison to hydrocarbons, ethanol has a high conductivity and contains

an active oxygen functionality. This can contribute to corrosion and wear
problems of some metal components. Furthermore, the suspension of water
within the ethanol/gasoline blend may enhance rusting and/or galvanic
corrosion. The tendency of ethanol to loosen varnish and gum deposits can
also have a significant impact. By loosening these deposits, ethanol may
accelerate wear of metallic components that are in regular contact with fuel by
scouring internal surfaces with suspended particles. The use of corrosion
inhibitors can help mitigate this problem although the compatibility of these
additives with ethanol/gasoline blends must be thoroughly evaluated.

Tables 1 and 2 provide an overview of materials that are either recommended for
use or should be avoided when handling ethanol or ethanol/gasoline blends.

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Table 1 Recommendations for Materials Considered for Use in Ethanol and

Ethanol/Gasoline Blend Applications [3]

Material Recommended Not Recommended

Metals Carbon steel with post-weld heat Zinc and galvanized materials
treatment of carbon steel piping
and internal lining of carbon steel Brass
2
tanks Copper
Stainless steel Lead/tin coated steel
Bronze Aluminium (may be an issue for
Aluminium E100)

Elastomers Buna-N (hoses & gaskets) Buna-N (seals only)

Fluorel Neoprene (seals only)
Fluorosilicone Urethane rubber
Neoprene (hoses & gaskets) Acrylonitrile-butadiene hoses
Polysulfide rubber Polybutene terephthalate
Viton
Polymers Acetal Polyurethane
Polypropylene Polymers containing alcohol groups
(such as alcohol based pipe dope)
Polyethylene
Nylon 66
Teflon
Fibreglass-reinforced polyester and
Fibreglass-reinforced plastic epoxy resins
Shellac
Others Paper Cork
Leather

This list is not comprehensive and the quality of the material must be appropriate for
the intended application. It is strongly advised that the manufacturers of these
products are consulted before ethanol or ethanol/gasoline blends are introduced.

2
During the past decade, there have been some reports of stress corrosion cracking of unlined carbon steel storage
tanks and non-heat-treated piping in contact with fuel ethanol. [8,9] At the time of this writing, the American Petroleum
Institute (API) is preparing a recommended practice related to ethanol storage.

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Table 2 Compatibility of Ethanol with Materials Commonly Used in Fuel

Distribution Systems [3]

Item Recommended Not Recommended

Containment Clay liners. Ethanol may dry
system (around out the liner and allow
tank and loading cracks to develop
racks)
Tanks used for E5 Mild steel Some lining materials
commonly used to prevent
Fibreglass-reinforced plastic (newer small leaks such as older
types) types of epoxy or polyester
resin-based materials. If a
tank is relined, the
manufacturer should be
contacted for advice.
Tanks used for May require a tank constructed of a
E100 special chemical resin
Pumps used for Carbon & ceramic seals
E100
Teflon-impregnated packing
materials
Pipe sealants used Teflon tape Alcohol based pipe sealants
for E5 and E100
Meters used for E5 When first converting to
ethanol/gasoline blends, it is
advisable to recalibrate meters after
10-14 days to ensure that the fuel
change has not caused any meters to
over-dispense
Meters used for Internal O-rings & seals should be
E100 selected that are specifically
designed for use with ethanol
Fuel Filters for E5 It may be necessary to change the Ethanol can dissolve the
fuel filter shortly after converting to glue in filter elements that
ethanol/gasoline blends. Once the are not specifically designed
dispensed fuel is clear and bright, the for this service
filter life should be similar to those in
regular gasoline applications.
Filters containing shellac
Hoses used for E5 No problems reported
Hoses used for Contact the manufacturer
E100
Nozzles used for No problems reported
E5

In this table:
• The term ‘E100’ refers to pure or denatured ethanol.
• The term ‘E5’ refers to blends of motor gasoline containing up to 5% v/v ethanol (EN228).

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2.8. SULPHATE ISSUES

Flow meter and pump deposits as well as filter plugging and injector sticking
incidents have been reported in the USA after they were exposed to some
ethanol/gasoline blends. According to work reported by ASTM, insoluble sulphates
have been implicated in these deposits and are believed to originate from sulphates
carried over from the ethanol manufacturing process. Specifications for fuel grade
ethanol should ensure against manufacturing impurities, including insoluble
sulphates.

2.9. DENATURANTS ISSUES

Customs and Excise agencies use denaturants to prevent the ingestion of ethanol
that is not intended for human consumption. Because there is evidence that some
denaturants can impact engine operation and performance, only denaturants that
have been demonstrated to have no detrimental effect on engine performance
should be used where they are allowed. Motor gasoline conforming to EN228
specifications that contains MTBE, ETBE, TBA, isobutanol, or isopropanol
denaturants is expected to show satisfactory performance.

2.10. TRANSPORT OF ETHANOL BLENDS

2.10.1. Transport via Multi-Product Pipelines

A review of current pipeline practices in other parts of the world indicates that the
pipeline shipment of ethanol/gasoline blends is not common practice. Pipeline
operating companies in the USA, for example, prohibit the shipment of
ethanol/gasoline blends.

If pipelines are to be used for this purpose, they must be completely dehydrated
prior to the shipment of ethanol/gasoline blends because of the affinity of ethanol for
residual water. Dehydrating a pipeline system is a major and potentially costly
endeavour and will require additional filtration and/or coalescer equipment to be
successfully completed.

If ethanol is transported via a pipeline system, more frequent cleaning and

inspection should occur due to the capacity of ethanol to pick-up dirt (rust,
sediments, etc.) throughout the system. Corrosion inhibitors that are compatible with
ethanol should be selected.

In multi-product pipelines, the potential contamination of jet fuel by ethanol is a very

serious concern. Because of the affinity of ethanol for water, higher concentrations
of dissolved water can be carried through the pipeline system and jet fuel
filter/coalescer performance may be impaired. On the other hand, in South Africa,
two trial shipments of ethanol/gasoline blends were carried out in multi-product
pipelines, without reported deterioration of the jet fuel quality.

Although the use of pipelines to transport ethanol/gasoline blends may not be

excluded, significant capital investments will be required to guarantee a completely
dry system, including additional filtration equipments and quality monitoring
systems.

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Prior to granting approval for such pipeline shipments, large scale trials should be
carried out with the active participation of all stakeholders, including the pipeline
operators, oil companies, aviation companies, and OEMs.

2.10.2. Transport by Road and Rail

In principle, the distribution of ethanol/gasoline blends by road truck and rail is done
in the same way as conventional motor gasoline. However, special precautions
should be taken to avoid contamination of the ethanol/gasoline blend with water,
dirt, rust, and gum. In particular, the ethanol/gasoline blend should not be mixed
with hydrocarbon-only fuel in order to avoid increases in vapour pressure.

2.10.3. Transport by Barge

Due to the affinity of ethanol for water, the transport of ethanol/gasoline blends by
barge should be avoided. If this is not possible, then extra precautions and
procedures should be put in place to ensure safety, cleanliness, and product
integrity following transport.

In particular, vessels that occasionally use product tanks as ballast water tanks
should not be used for transporting ethanol/gasoline blends. Any commingling of
ethanol/gasoline blends and water should be strictly avoided.

2.11. SAFETY & FIRE FIGHTING MEASURES

2.11.1. Safe Handling

Safety precautions and equipment for storing and handling ethanol/gasoline blends
are similar to those used for conventional gasoline. Protective equipment including
gloves should always be worn. Skin exposed to fuel should be washed with soapy
water. The relevant Safety Data Sheet (SDS) should also be reviewed for
recommendations on safe handling, type of gloves, and related procedures before
beginning work with ethanol and with ethanol/gasoline blends.

2.11.2. Surface Spills and Leaks

Spills and underground leaks of ethanol/gasoline blends should be treated in the

same manner as motor gasoline spills and leaks, including notification of the proper
authorities. The supplier’s SDS should also be reviewed for recommendations on
spill clean-up procedures.

2.11.3. Fire Protection and Fire-Fighting Agents for Fires Involving

Ethanol/Gasoline Blends

Personnel should approach an ethanol/gasoline blend fire with the same caution as
they would use in approaching a conventional gasoline fire, and similar fire-fighting
techniques should be used.

The use of alcohol resistant foams is required when fighting fires involving fuels
containing high levels of ethanol. For fighting fires involving gasolines containing up
to 10% v/v ethanol, such foams may not be required but it is strongly advised that

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responsible personnel review their specific operations and use appropriate

equipment based on local safety recommendations and requirements.

Fires involving pure ethanol do not produce smoke and the flames are difficult to
see in daylight.

2.11.4. Storage

Pure ethanol can be stored in fixed roof tanks with or without an internal floating
cover (IFC)3. Tanks with external floating covers can allow some rain water to enter
the tank and are not recommended for storing ethanol.

The vapour concentration above 100% liquid ethanol will be in the flammable range
when the liquid temperature is between about 12 and 43ºC. Because impurities in
the ethanol can alter this range, however, it is good engineering practice to assume
that the vapour phase above fuel-grade ethanol is always in the flammable range
and procedures and equipment should be used that ensure safe storage conditions.
The type of vent on a fixed roof tank will not greatly affect the average flammability
condition whether the vents are open or Pressure/Vacuum (P/V) vents. (A P/V vent
is a venting device that reduces the free flow of air and vapours in and out of the
tank).

When used for storing pure ethanol, an internal floating roof tank with a P/V vent on
the fixed roof is likely to be in the flammable range. An IFC with air scoops (that is,
with slits in the tank walls to allow free venting, conforming to API 650H guidelines
where permitted) will probably be outside of the flammable range as long as the
floating roof seals are in good condition and the number and size of the vents are
appropriate.

For this reason, procedures, similar to those used for gasoline storage, should be
used to ensure against ignition, especially when fixed roof tanks are used to store
liquid ethanol. These procedures can include the use of inerting gas systems to
avoid a flammable mixture in the vapour space although this approach may not be
practical in all situations. Ethanol and blended fuel storage must comply with
prevailing legislation.

2.11.5. Sources of Ignition

The presence of ethanol does not substantially increase the risk of static electricity
since ethanol has a high electrical conductivity. Lightning could be a problem but a
well-grounded metal tank with a well maintained P/V vent or flame arrestor on the
vent is considered safe. Excessive friction could cause ignition inside an internal
floating roof tank if, for example, the floating roof were to develop a mechanical
problem.

Obviously, hot repair work or other human activities near the open vent of an in-
service tank must be avoided because these practices could cause ignition to occur.
Procedures, similar to those used for conventional gasoline tanks, should be in
place to avoid these problems.

3
An internal floating cover (IFC) is one in which the cover deck is located inside the fixed roof storage
tank in order to reduce tank vapour emissions.

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2.11.6. Drain or Waste Water Handling

Ethanol can be difficult to remove from drains and waste water because it is very
soluble in water. For this reason, the only way to efficiently remove ethanol is
through biological treatment.

If the bacteria in treatment facilities have not been acclimatised to ethanol, much of
the ethanol will pass through the treatment plant before it is degraded. Several
weeks to a month may be required before a treatment plant can efficiently process
ethanol-containing waste streams. Facilities can gradually increase the ethanol
content in their waste water system as the bacteria become more efficient at
degrading ethanol. It is important to test degradation performance in the laboratory
and analyse the plant effluent for ethanol content over time in order to determine the
degradation rate.

Because terminals do not usually have biological treatment facilities, ethanol will
most likely pass through the mechanical treatments that are commonly used. If the
terminal sends its waste water to a municipal treatment plant, it is important to check
with the treatment plant operators whether their facility can handle ethanol-
containing waste.

In any case, the disposal of drain or waste water must be done in accordance with
all local regulations and permits.

2.12. ADDITIVE EFFECTS

In order to ensure fit-for-purpose motor gasolines, corrosion inhibitors should be

added to fuel grade ethanol by ethanol producers, distributors, and gasoline
blenders. Only corrosion inhibitors that are effective in such applications and
compatible with hydrocarbon-only gasolines should be used for this purpose.

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3. BLENDING GUIDELINES

3.1. REFINERY BLENDING

Blending ethanol at the refinery is not preferred because of problems that can occur
with the subsequent transport and storage of the ethanol/gasoline blend. Refinery
blending may be appropriate, however, when ethanol/gasoline blends are directly
supplied to the loading rack from the refinery.

3.2. TERMINAL BLENDING

Direct blending at the loading rack is the best approach to overcome the transport
and handling issues associated with ethanol-containing fuels. To do this, the refinery
must produce a special BOB (see Section 2.4) and supply it to the terminal. This
typically results in additional costs for injection equipment and ethanol storage, as
well as an increase in truck movements.

For product quality reasons, terminals should be designated either as ethanol-

blending or ethanol-free locations (unless they have segregated systems for storage
and handling) and their service should not routinely change.

Blending ethanol at low ambient temperatures is not believed to cause any

additional problems that are not also encountered at higher ambient temperatures.

The commingling of ethanol and motor gasoline can result in a small volumetric
increase of the blend. This increase should be taken into account when considering
product volumetric measurement and accounting.

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4. GLOSSARY

API American Petroleum Institute

BOB Blendstock for Oxygenate Blending
DVPE Dry Vapour Pressure Equivalent
E70 % evaporated at 70C
E100 % evaporated at 100C
EN228 European Standard for motor gasoline containing up to 5% v/v
ethanol
ETBE Ethyl Tertiary Butyl Ether
EtOH Ethanol
EU European Union
IFC Internal Floating Cover
MON Motor Octane Number
MTBE Methyl Tertiary Butyl Ether
OEM Original Equipment Manufacturer
P/V Pressure/Vacuum
RON Research Octane Number
RUP Regular Unleaded Petrol
SDS Safety Data Sheet
SUP Super Unleaded Petrol
TBA Tertiary Butyl Alcohol
ULG Unleaded Gasoline

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5. ACKNOWLEDGMENTS

FE/STF-24 wishes to acknowledge the contributions to this report from

Dr. Neville D. Thompson, who was the CONCAWE Technical Coordinator for Fuels
and Emissions from 2000-2006. Before his untimely death in August, 2006, Neville
was instrumental in guiding STF-24 activities and ensuring a smooth start to this
project. We will always remember him as a good friend, an esteemed colleague,
and a true professional in his field.

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6. REFERENCES

1. RFA (2005) Fuel ethanol – industry guidelines, specifications and procedures. RFA
Publ. No. 960501. Washington DC: Renewable Fuels Association

2. API (2001) Alcohols and ethers – a technical assessment of their application as

fuels and fuel components. API Publ. 4261, 3rd edition. Washington DC: American
Petroleum Institute

3. ADM (2001) Fuel ethanol – technical information. Decatur IL: Archer Daniels
Midland Company

4. Owen, K. and Coley, T. (1995) Automotive fuels reference book (2nd edition).
Warrendale PA: Society of Automotive Engineers

5. NESCAUM (2001) Health, environmental, and economic impacts of adding ethanol

to gasoline in the Northeast States. Vol. 2: Air quality, health, and economic
impacts. Boston MA: Northeast States for Coordinated Air Use Management

6. Guibet, J.-C. (1999) Fuels and engines. Vol.1, p. 193-200, p. 220-224, p. 234-243.
Paris: Éditions Technip

7. Terschek, R. and Ludzay, J. (2005) Laboratory test programme on the addition of

ethanol to automotive fuels. Research Report No. 645. Hamburg: DGMK

8. Kane, R.D. et al (2004) Stress corrosion cracking in fuel ethanol: a newly

recognized phenomenon. Paper No. 04543. Houston TX: NACE International

9. API (2007) Stress corrosion cracking of carbon steel in fuel grade ethanol: review,
experience survey, field monitoring, and laboratory testing. API TR 939-D,
2nd edition. Washington DC: American Petroleum Institute

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